Herbicidal compounds

ABSTRACT

The present invention relates to a method of controlling plants or inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I): wherein A 1 , A 2 , A 3 , A 4 , R 3 , R 4  and R 5  are as defined in claim 1; or a salt or N-oxide thereof. Furthermore, the present invention relates to processes for preparing compounds of formula (I), to intermediates used in the preparation of compounds of formula (I), to herbicidal compositions comprising compounds of formula (I) and to certain novel pyridopyridines, pyridodiazines and pyridotriazines.

The present invention relates to novel herbicidal pyridopyridines,pyridodiazines and pyridotriazines, to processes for their preparation,to compositions comprising these compounds, and to their use incontrolling plants or in inhibiting plant growth.

Certain pyridopyridines were disclosed as intermediates in the synthesisof fungicidal compounds, for example, in WO 04/056824. Certainpyridopyrimidines were disclosed as intermediates in the synthesis offungicidal compounds, for example, in WO 04/056825 and WO 04/056826.Certain pyridotriazines were disclosed as intermediates in the synthesisof fungicidal compounds, for example, in WO 04/056829. Certainpyridopyridines and pyridopyrimidines were disclosed as fungicidalcompounds, for example, in WO 05/010000. Certain pyridopyridines weredisclosed as pharmaceutical compounds, for example, in WO 95/30676, JP07053546 and WO 01/62252. Certain pyridodiazines and pyridotriazineswere disclosed as pharmaceutical compounds, for example, in WO02/076396. Certain pyridopyrimidines were disclosed as pharmaceuticalcompounds, for example, in WO 02/076946, WO 06/124490 and WO 07/044,813.Certain pyridopyridines and pyridopyrimidines were disclosed aspharmaceutical compounds, for example, in WO 96/22990, WO 02/018383, WO03/066630 and WO 07/136,465. Certain pyridopyridines were disclosed inJournal of Heterocyclic Chemistry (1993), 30(4), 909-12 and Bioorganic &Medicinal Chemistry (2001), 9(8), 2061-2071.

It has now surprisingly been found that certain pyridopyridines,pyridodiazines and pyridotriazines display excellent herbicidal andgrowth-inhibiting properties.

The present invention therefore provides a method of controlling plantswhich comprises applying to the plants or to the locus thereof aherbicidally effective amount of a compound of formula (I)

whereinA¹, A², A³ and A⁴ are independently C—R¹ or N, provided at least one ofA¹, A², A³ and A⁴ is N, and provided that if A¹ and A⁴ are both N, A²and A³ are not both C—R¹;each R¹ is independently hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, halo,cyano, hydroxy, C₁-C₄alkoxy, C₁-C₄alkylthio, aryl or aryl substituted byone to five R⁶, which may be the same or different, or heteroaryl orheteroaryl substituted by one to five R⁶, which may be the same ordifferent;R³ is hydrogen, C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₂-C₁₀alkenyl,C₂-C₄haloalkenyl, C₂-C₁₀alkynyl, C₂-C₄haloalkynyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₆alkyl-, C₁-C₁₀alkoxy-C₁-C₆alkyl-,C₁-C₁₀cyanoalkyl-, C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different;R⁴ is aryl or aryl substituted by one to five R⁸, which may be the sameor different, or heteroaryl or heteroaryl substituted by one to four R⁸,which may be the same or different;R⁵ is hydroxy or a group which can be metabolised to a hydroxy group;each R⁶, R⁷ and R⁸ is independently halo, cyano, nitro, C₁-C₁₀alkyl,C₁-C₄haloalkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, hydroxy, C₁-C₁₀alkoxy,C₁-C₄haloalkoxy, C₁-C₁₀alkoxy-C₁-C₄alkyl-, C₃-C₇cycloalkyl,C₃-C₇cycloalkoxy, C₃-C₇cycloalkyl-C₁-C₄alkyl-,C₃-C₇cycloalkyl-C₁-C₄alkoxy-, C₁-C₆alkylcarbonyl-, formyl,C₁-C₄alkoxycarbonyl-, C₁-C₄alkylcarbonyloxy-, C₁-C₁₀alkylthio-,C₁-C₄haloalkylthio-, C₁-C₁₀alkylsulfinyl-, C₁-C₄haloalkylsulfinyl-,C₁-C₁₀alkylsulfonyl-, C₁-C₄haloalkylsulfonyl-, amino, C₁-C₁₀alkylamino-,di-C₁-C₁₀alkylamino-, C₁-C₁₀alkylcarbonylamino-, aryl or arylsubstituted by one to three R¹³, which may be the same or different,heteroaryl or heteroaryl substituted by one to three R¹³, which may bethe same or different, aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein thearyl moiety is substituted by one to three R¹³, which may be the same ordifferent, heteroaryl-C₁-C₄alkyl- or heteroaryl-C₁-C₄alkyl- wherein theheteroaryl moiety is substituted by one to three R¹³, which may be thesame or different, aryloxy- or aryloxy-substituted by one to three R¹³,which may be the same or different, heteroaryloxy- orheteroaryloxy-substituted by one to three R¹³, which may be the same ordifferent, arylthio- or arylthio-substituted by one to three R¹³, whichmay be the same or different, or heteroarylthio- orheteroarylthio-substituted by one to three R¹³, which may be the same ordifferent; andeach R¹³ is independently halo, cyano, nitro, C₁-C₆alkyl, C₁-C₆haloalkylor C₁-C₆alkoxy; or a salt or N-oxide thereof.

The compounds of formula (I) may exist in different geometric or opticalisomers or tautomeric forms. This invention covers all such isomers andtautomers and mixtures thereof in all proportions as well as isotopicforms such as deuterated compounds.

For example, a compound of formula (Ia), i.e. a compound of formula (I)wherein R³ is hydrogen and R⁵ is hydroxy, can be drawn in at least fivetautomeric forms.

Some of these compounds exhibit good herbicidal activity. Additionally,these compounds can be used as intermediates for the synthesis ofcompounds of the formula (Ib), (Ic) and (Id).

For example, a compound of formula (Ib), i.e. a compound of formula (I)wherein R³ is hydrogen and R⁵ is as defined for compounds of formula (I)other than hydroxy, can be drawn in at least two tautomeric forms.

Some of these compounds exhibit good herbicidal activity. Additionally,these compounds can be used as intermediates for the synthesis ofcompounds of the formula (Ia), (Ic) and (Id).

A compound of formula (Ic), i.e. a compound of formula (I) wherein R³ isas defined for compounds of formula (I) other than hydrogen and R⁵ is asdefined for compounds of formula (I) other than hydroxy, can be drawn inonly one tautomeric form.

Most of these compounds exhibit excellent herbicidal activity.Additionally, these compounds can be used as intermediates for thesynthesis of compounds of the formula (Ia), (Ib) and (Id).

A compound of formula (Id), i.e. a compound of formula (I) wherein R³ isas defined for compounds of formula (I) other than hydrogen and R⁵ ishydroxy, can be drawn in three tautomeric forms.

Most of these compounds exhibit good herbicidal activity. Additionally,these compounds can be used as intermediates for the synthesis ofcompounds of the formula (Ia), (Ib) and (Ic).

Each alkyl moiety (either alone or as part of a larger group, such asalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl) is a straight or branched chain and is, forexample, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl. Thealkyl groups are preferably C₁ to C₆ alkyl groups, more preferably C₁-C₄and most preferably C₁-C₃ alkyl groups.

Alkenyl and alkynyl moieties (either alone or as part of a larger group,such as alkenyloxy or alkynyloxy) can be in the form of straight orbranched chains, and the alkenyl moieties, where appropriate, can be ofeither the (E)- or (Z)-configuration. Examples are vinyl, allyl,prop-2-enyl and propargyl. The alkenyl and alkynyl groups are preferablyC₂ to C₆ alkenyl or alkynyl groups, more preferably C₂-C₄ and mostpreferably C₂-C₃ alkenyl or alkynyl groups.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups (either alone or as part of a larger group, such ashaloalkoxy or haloalkylthio) are alkyl groups which are substituted withone or more of the same or different halogen atoms and are, for example,—CF₃, —CF₂Cl, —CHF₂, —CH₂CF₃ or —CH₂CHF₂. Haloalkenyl and haloalkynylgroups (either alone or as part of a larger group, such ashaloalkenyloxy or haloalkynyloxy) are alkenyl and alkynyl groups,respectively, which are substituted with one or more of the same ordifferent halogen atoms and are, for example, —CH═CF₂, —CF═CH₂ or—C≡CCl.

Cyanoalkyl groups are alkyl groups which are substituted with one ormore cyano groups, for example, cyanomethyl or 1,3-dicyanopropyl.

Cycloalkyl groups can be in mono- or bi-cyclic form and may optionallybe substituted by one or more methyl groups. The cycloalkyl groupspreferably contain 3 to 8 carbon atoms, more preferably 3 to 6 carbonatoms. Examples of monocyclic cycloalkyl groups are cyclopropyl,1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl.

In the context of the present specification the term “aryl” refers to aring system which may be mono-, bi- or tricyclic. Examples of such ringsinclude phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. Apreferred aryl group is phenyl.

The term “heteroaryl” refers to an aromatic ring system containing atleast one heteroatom and consisting either of a single ring or of two ormore fused rings. Preferably, single rings contain up to three andbicyclic systems up to four heteroatoms which are preferably chosen fromnitrogen, oxygen and sulfur. Examples of monocyclic groups includepyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl,thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl.More preferred monocyclic groups are pyridyl, pyrimidinyl, thiophenyl,isoxazolyl, oxadiazolyl, and thiazolyl. Examples of bicyclic groups arebenzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl,isoquinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1,5-a]pyrimidinyl.More preferred bicyclic groups are quinolinyl and isoquinolinyl.

The term “heterocyclyl” is defined to include heteroaryl and in additiontheir unsaturated or partially unsaturated analogues such as4,5,6,7-tetrahydro-benzothiophenyl, chromen-4-onyl, 9H-fluorenyl,3,4-dihydro-2H-benzo-1,4-dioxepinyl, 2,3-dihydro-benzofuranyl,piperidinyl, 1,3-dioxolanyl, 1,3-dioxanyl, 4,5-dihydro-isoxazolyl,tetrahydrofuranyl and morpholinyl.

The term “herbicide” as used herein means a compound that controls ormodifies the growth of plants. The term “herbicidally effective amount”means the quantity of such a compound or combination of such compoundsthat is capable of producing a controlling or modifying effect on thegrowth of plants. Controlling or modifying effects include all deviationfrom natural development, for example: killing, retardation, leaf burn,albinism, dwarfing and the like. The term “plants” refers to allphysical parts of a plant, including seeds, seedlings, saplings, roots,tubers, stems, stalks, foliage, and fruits. The term “locus” is intendedto include soil, seeds, and seedlings, as well as establishedvegetation. The term “metabolism” as used herein means the conversion orbreakdown of a substance from one form to another by a living organism,in particular in a plant (in planta).

The term “salt” as used herein means a compound of formula (I) which hasa negative charge, for example, on an oxygen atom of a hydroxyl or of acarboxyl group, or a compound of formula (I) which has a positivecharge, for example, on a nitrogen atom in a nitrogen-containingheteroaryl group, for example if a such a nitrogen is quarternised byalkylation. The counter ion is necessarily of the opposite charge. Wherethe counter ion needs to be a cation the counter ion could be, forexample, an alkali metal such as sodium or potassium, or an alkalineearth metal such as magnesium and calcium, or a quaternary ammonium basesuch as ammonium and tetramethylammonium. Where the counter ion needs tobe a cation the counter ion could be, for example, hydroxide, or ahalide such as chloride or bromide.

The compounds of formula (I) according to the invention also includehydrates which may be formed, for example, during salt formation.

Preferred values of A¹, A², A³, A⁴, R¹, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³ and R¹⁴ are, in any combination, as set out below.

Preferably up to three of A¹, A², A³ and A⁴ are N.

More preferably up to two of A¹, A², A³ and A⁴ are N.

Most preferably one of A¹, A², A³ and A⁴ is N.

Preferably each R¹ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, halo, cyano,hydroxy or C₁-C₄alkoxy.

More preferably each R¹ is hydrogen, C₁-C₄alkyl, halo, cyano or hydroxy.

Even more preferably each R¹ is hydrogen, methyl, chloro or bromo.

Yet even more preferably each R¹ is hydrogen or chloro.

Most preferably each R¹ is hydrogen.

Preferably R³ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl or C₂-C₄haloalkynyl. Examples of suchpreferred groups for R³ are hydrogen, methyl, ethyl, n-propyl,iso-propyl, n-butyl, 2-methyl-propyl, 2-fluoro-ethyl,2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, allyl, but-3-en-1-yl orpropargyl.

More preferably R³ is hydrogen, C₁-C₂alkyl, C₁-C₂haloalkyl, C₂-C₃alkenylor C₂-C₃alkynyl. Examples of such more preferred groups for R³ arehydrogen, methyl, ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl,allyl or propargyl.

Most preferably R³ is hydrogen, C₁-C₂alkyl, C₁-C₂haloalkyl orC₂-C₃alkynyl. Examples of such most preferred groups for R³ arehydrogen, methyl, ethyl, 2,2-difluoro-ethyl or propargyl.

In one preferred embodiment R³ is 2,2-difluoro-ethyl.

Preferably R⁴ is aryl or aryl substituted by one to four R⁸, which maybe the same or different, or heteroaryl or heteroaryl substituted by oneto three R⁸, which may be the same or different.

More preferably R⁴ is aryl substituted by two to three R⁸, which may bethe same or different, or R⁴ is a monocyclic heteroaryl, containing upto two heteroatoms, substituted by one to three R⁸, which may be thesame of different, or R⁴ is a bicyclic heteroaryl, containing up tothree heteroatoms, substituted by one to three R⁸, which may be the sameof different.

Most preferably R⁴ is phenyl substituted by two to three R⁸, or R⁴ ispyridyl, pyrimidinyl, thiophenyl, isoxazolyl, oxadiazolyl, or thiazolyl,substituted by one to three R⁸, which may be the same or different, orR⁴ is quinolinyl or isoquinolinyl, substituted by one to three R⁸, whichmay be the same or different.

In one preferred embodiment R⁴ is 2,5-bis-(trifluoromethyl)-phenyl.

In one preferred embodiment R⁴ is 3-bromo-2-chloro-6-fluoro-phenyl.

In one preferred embodiment R⁴ is 2-chloro-3,6-difluoro-phenyl.

In one preferred embodiment R⁴ is 2-chloro-5-fluoro-phenyl.

In one preferred embodiment R⁴ is 2-chloro-5-trifluoromethyl-phenyl.

In one preferred embodiment R⁴ is 2-chloro-6-trifluoromethyl-phenyl.

In one preferred embodiment R⁴ is 2,3-dichloro-6-fluoro-phenyl.

In one preferred embodiment R⁴ is 2,6-dichloro-phenyl.

In one preferred embodiment R⁴ is2,6-dichloro-4-trifluoromethoxy-phenyl.

In one preferred embodiment R⁴ is 2,3,6-trichloro-phenyl.

In one preferred embodiment R⁴ is 3,5-dichloro-pyrid-2-yl.

In one preferred embodiment R⁴ is 3,5-dichloro-pyrid-4-yl.

In one preferred embodiment R⁴ is 2,6-dichloro-pyrid-3-yl.

In one preferred embodiment R⁴ is 2,4-dichloro-pyrid-3-yl.

In one preferred embodiment R⁴ is 4,6-dichloro-pyrid-3-yl.

In one preferred embodiment R⁴ is 2,5-dichloro-pyrid-4-yl.

In one preferred embodiment R⁴ is 3-trifluoromethyl-isoxazol-5-yl.

In one preferred embodiment R⁴ is 3-methyl-1,2,4-oxadiazol-5-yl.

In one preferred embodiment R⁴ is 2-chloro-4-methyl-thiazol-5-yl.

Preferably R⁵ is hydroxy, R⁹-oxy-, R¹⁰-carbonyloxy-, tri-R¹¹-silyloxy-or R¹²-sulfonyloxy-, wherein

R⁹ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or aryl-C₁-C₄alkyl- oraryl-C₁-C₄alkyl-wherein the aryl moiety is substituted by one to fivesubstituents independently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy;R¹⁰ is C₁-C₁₀alkyl, C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkyl-C₁-C₁₀alkyl-,C₁-C₁₀haloalkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₄alkoxy-C₁-C₁₀alkyl-,C₁-C₄alkylthio-C₁-C₄alkyl-, C₁-C₁₀alkoxy, C₂-C₁₀alkenyloxy,C₂-C₁₀alkynyloxy, C₁-C₁₀alkylthio-, N—C₁-C₄alkyl-amino-,N,N-di-(C₁-C₄alkyl)-amino-, aryl or aryl substituted by one to threeR¹⁴, which may be the same or different, heteroaryl or heteroarylsubstituted by one to three R¹⁴, which may be the same or different,aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein the aryl moiety issubstituted by one to three R¹⁴, which may be the same or different,heteroaryl-C₁-C₄alkyl- or heteroaryl-C₁-C₄alkyl- wherein the heteroarylmoiety is substituted by one to three R¹⁴, which may be the same ordifferent, aryloxy- or aryloxy-substituted by one to three R¹⁴, whichmay be the same or different, heteroaryloxy- orheteroaryloxy-substituted by one to three R¹⁴, which may be the same ordifferent, arylthio- or arylthio-substituted by one to three R¹⁴, whichmay be the same or different, or heteroarylthio- orheteroarylthio-substituted by one to three R¹⁴, which may be the same ordifferent;each R¹¹ is independently C₁-C₁₀alkyl or phenyl or phenyl substituted byone to five substituents independently selected from halo, cyano, nitro,C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy;R¹² is C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, or phenyl or phenyl substituted byone to five substituents independently selected from halo, cyano, nitro,C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-Colkoxy; andeach R¹⁴ is independently halo, cyano, nitro, C₁-C₁₀alkyl,C₁-C₄haloalkyl, C₁-C₁₀alkoxy, C₁-C₄alkoxycarbonyl-, C₁-C₄haloalkoxy,C₁-C₁₀alkylthio-, C₁-C₄haloalkylthio-, C₁-C₁-C₄haloalkylsulfinyl-,C₁-C₄haloalkylsulfonyl-, aryl or aryl substituted by one to fivesubstituents independently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy, or heteroaryl or heteroaryl substitutedby one to four substituents independently selected from halo, cyano,nitro, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy.

More preferably R⁵ is hydroxy, R⁹-oxy- or R¹⁰-carbonyloxy-.

Even more preferably R⁵ is hydroxy, C₁-C₄alkoxy, C₁-C₄alkenyloxy,C₁-C₄alkynyloxy, aryl-C₁-C₄alkoxy or aryl-C₁-C₄alkoxy wherein the arylmoiety is substituted by one to three R¹⁴, which may be the same ordifferent, heteroaryl-C₁-C₄alkoxy or heteroaryl-C₁-C₄alkoxy wherein theheteroaryl moiety is substituted by one to three R¹⁴, which may be thesame or different, C₁-C₄alkylcarbonyloxy-, C₃-C₆cyclo-alkylcarbonyloxy-,C₃-C₁₀cycloalkyl-C₁-C₁₀alkylcarbonyloxy-, C₁-C₄haloalkylcarbonyl-oxy-,C₂-C₄alkenylcarbonyloxy-, C₂-C₄alkynylcarbonyloxy-,C₁-C₄alkoxy-C₁-C₄alkyl-carbonyloxy-,C₁-C₄alkylthio-C₁-C₄alkylcarbonyloxy-, C₁-C₄alkoxycarbonyloxy-,C₂-C₄alkenyloxycarbonyloxy-, C₂-C₄alkynyloxycarbonyloxy-,C₁-C₄alkylthiocarbonyloxy-, N—C₁-C₄alkyl-aminocarbonyloxy-,N,N-di-(C₁-C₄alkyl)-aminocarbonyloxy-, aryl-carbonyloxy- orarylcarbonyloxy-substituted by one to three R¹⁴, which may be the sameor different, heteroarylcarbonyloxy- orheteroarylcarbonyloxy-substituted by one to three R¹⁴, which may be thesame or different, aryl-C₁-C₄alkylcarbonyloxy- oraryl-C₁-C₄alkylcarbonyloxy- wherein the aryl moiety is substituted byone to three R¹⁴, which may be the same or different,heteroaryl-C₁-C₄alkylcarbonyloxy- or heteroaryl-C₁-C₄alkylcarbonyloxy-wherein the heteroaryl moiety is substituted by one to three R¹⁴, whichmay be the same or different, aryloxycarbonyloxy- oraryloxycarbonyloxy-substituted by one to three R¹⁴, which may be thesame or different, heteroaryloxy-carbonyloxy- orheteroaryloxycarbonyloxy-substituted by one to three R¹⁴, which may bethe same or different, arylthiocarbonyloxy- orarylthiocarbonyloxy-substituted by one to three R¹⁴, which may be thesame or different, or heteroarylthiocarbonyloxy- orheteroarylthiocarbonyloxy-substituted by one to three R¹⁴, which may bethe same or different. Examples of preferred groups for R⁵ are hydroxy,methoxy, ethoxy, allyloxy, propargyloxy, benzyloxy, methylcarbonyloxy-,ethylcarbonyloxy-, iso-propylcarbonyl-oxy-, n-propylcarbonyloxy-,but-2-ylcarbonyloxy-, 2-methyl-propylcarbonyloxy-,tert-butylcarbonyloxy-, cyclopropylcarbonyloxy-,cyclopentyl-methylcarbonyloxy-, chloromethylcarbonyloxy-,trifluoromethylcarbonyloxy-, allylcarbonyloxy-,(E)-prop-1-en-1-ylcarbonyloxy-, 2-methyl-prop-1-en-1-ylcarbonyloxy-,methoxymethylcarbonyl-oxy-, ethoxycarbonyloxy-, tert-butoxycarbonyloxy-,but-2-yn-1-yloxycarbonyloxy-, ethylthiocarbonyloxy-,N,N-diethylaminocarbonyloxy-, phenylcarbonyloxy-,3-methoxy-phenylcarbonyloxy-, 4-nitro-phenylcarbonyloxy-,benzylcarbonyloxy-, furan-2-yl-carbonyloxy-,2,5-dimethyl-furan-3-ylcarbonyloxy-, thiophen-2-ylcarbonyloxy-,3,5-dimethyl-isoxazol-4-ylcarbonyloxy-, and1-phenyl-prop-1-ylcarbonyloxy-.

Yet even more preferably R⁵ is hydroxy, C₁-C₄alkylcarbonyloxy-,C₃-C₆cyclo-alkylcarbonyloxy-, C₂-C₄alkenylcarbonyloxy-,C₂-C₄alkynylcarbonyloxy-, C₁-C₄alkoxycarbonyloxy-,C₂-C₄alkenyloxycarbonyloxy-, C₂-C₄alkynyloxycarbonyloxy- orC₁-C₄alkylthiocarbonyloxy-. Examples of more preferred groups for R⁵ arehydroxy, methylcarbonyloxy-, ethylcarbonyloxy-, iso-propylcarbonyloxy-,n-propylcarbonyloxy-, but-2-ylcarbonyloxy-, 2-methyl-propylcarbonyloxy-,tert-butylcarbonyloxy-, cyclopropylcarbonyloxy-, allylcarbonyloxy-,(E)-prop-1-en-1-ylcarbonyloxy-, 2-methyl-prop-1-en-1-ylcarbonyloxy-,ethoxycarbonyloxy-, tert-butoxycarbonyloxy-,but-2-yn-1-yloxycarbonyloxy-, and ethylthiocarbonyloxy-.

Most preferably R⁵ is hydroxy, C₁-C₄alkylcarbonyloxy-,C₁-C₄alkoxycarbonyloxy- or C₁-C₄alkylthiocarbonyloxy-. Examples of mostpreferred groups for R⁵ are hydroxy, methylcarbonyloxy-,ethylcarbonyloxy-, iso-propylcarbonyloxy-, n-propyl-carbonyloxy-,but-2-ylcarbonyloxy-, 2-methyl-propylcarbonyloxy-,tert-butylcarbonyl-oxy-, ethoxycarbonyloxy-, and ethylthiocarbonyloxy-.

In one preferred embodiment R⁵ is hydroxy.

In one preferred embodiment R⁵ is R⁹-oxy-, wherein R⁹ is C₁-C₁₀alkyl,C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl-wherein the aryl moiety is substituted by one to five substituentsindependently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy. Such R⁵ groups may be metabolised,preferably in planta, to give the corresponding compound wherein R⁵ ishydroxy.

In one preferred embodiment R⁵ is R¹⁰-carbonyloxy-, wherein R¹⁰ isC₁-C₁₀alkyl, C₃-C₁₀cycloalkyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkenyl,C₂-C₁₀alkynyl, C₁-C₄alkoxy-C₁-C₁₀alkyl-, C₁-C₄alkylthio-C₁-C₄alkyl-,C₁-C₁₀alkoxy, C₂-C₁₀alkenyloxy, C₂-C₁₀alkynyloxy, N—C₁-C₄alkyl-amino-,N,N-di-(C₁-C₄alkyl)-amino-, aryl or aryl substituted by one to threeR¹⁴, which may be the same or different, heteroaryl or heteroarylsubstituted by one to three R¹⁴, which may be the same or different,aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein the aryl moiety issubstituted by one to three R¹⁴, which may be the same or different,heteroaryl-C₁-C₄alkyl- or heteroaryl-C₁-C₄alkyl- wherein the heteroarylmoiety is substituted by one to three R¹⁴, which may be the same ordifferent, aryloxy- or aryloxy-substituted by one to three R¹⁴, whichmay be the same or different, heteroaryloxy- orheteroaryloxy-substituted by one to three R¹⁴, which may be the same ordifferent, arylthio- or arylthio-substituted by one to three R¹⁴, whichmay be the same or different, or heteroarylthio- orheteroarylthio-substituted by one to three R¹⁴, which may be the same ordifferent; and each R¹⁴ is independently halo, cyano, nitro,C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₁-C₁₀alkoxy, C₁₀alkoxycarbonyl-,C₁-C₄haloalkoxy, C₁-C₄haloalkylthio-, C₁-C₁₀alkylsulfinyl-,C₁-C₄haloalkylsulfinyl-, C₁-C₁₀alkylsulfonyl-, C₁-C₄haloalkylsulfonyl-,aryl or aryl substituted by one to five substituents independentlyselected from halo, cyano, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl orC₁-C₆alkoxy, or heteroaryl or heteroaryl substituted by one to foursubstituents independently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy. Such R⁵ groups may be metabolised,preferably in planta, to give the corresponding compound wherein R⁵ ishydroxy.

In one preferred embodiment R⁵ is iso-propylcarbonyloxy- ortert-butyl-carbonyloxy-.

Preferably each R⁶ is independently halo, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy or C₁-C₄haloalkoxy. Examples of such preferred groups for R⁶are chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy ortrifluoromethoxy.

Preferably each R⁷ is independently halo, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy or C₁-C₄haloalkoxy. Examples of such preferred groups for R⁷are chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy andtrifluoromethoxy.

Most preferably each R⁷ is independently halo, C₁-C₄alkyl,C₁-C₄haloalkyl or C₁-C₄alkoxy. Examples of such preferred groups for R⁷are chloro, fluoro, methyl, ethyl, trifluoromethyl and methoxy.

Preferably each R⁸ is independently halo, cyano, nitro, C₁-C₁₀alkyl,C₁-C₄haloalkyl, C₁-C₁₀alkoxy, C₁-C₄alkoxycarbonyl-, C₁-C₄haloalkoxy,C₁-C₁₀alkylthio-, C₁-C₄haloalkylthio-, C₁-C₁₀alkylsulfinyl-,C₁-C₄haloalkylsulfinyl-, C₁-C₁₀alkylsulfonyl- orC₁-C₄haloalkylsulfonyl-.

More preferably each R⁸ is independently halo, cyano, nitro,C₁-C₁₀alkyl, C₄haloalkyl, C₁-C₁₀alkoxy, C₁-C₄haloalkoxy, C₁-C₁₀alkylthioor C₁-C₄haloalkylthio. Examples of such more preferred groups for R⁸ areiodo, bromo, chloro, fluoro, cyano, nitro, methyl, ethyl,trifluoromethyl, methoxy, trifluoromethoxy or trifluoromethylthio.

Most preferably each R⁸ is independently halo, C₁-C₁₀alkyl,C₁-C₄haloalkyl, C₁-C₁₀alkoxy or C₁-C₄haloalkoxy. Examples of such mostpreferred groups for R⁸ are bromo, chloro, fluoro, methyl, ethyl,trifluoromethyl, methoxy or trifluoromethoxy. Preferably R⁹ isC₂-C₁₀alkenyl, C₂-C₁₀alkynyl, aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl-wherein the aryl moiety is substituted by one to three R¹³, which may bethe same or different.

More preferably R⁹ is C₃-C₄alkenyl, or C₃-C₄alkynyl, benzyl or benzylwherein the phenyl moiety is substituted by one to three R¹³, which maybe the same or different.

Even more preferably R⁹ is allyl, propargyl or benzyl.

Most preferably R⁹ is allyl.

Preferably R¹⁰ is C₁-C₄alkyl, C₃-C₆cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl,C₂-C₄alkynyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy, C₁-C₄alkylthio,N—C₁-C₄alkyl-amino, N,N-di-(C₁-C₄alkyl)-amino, aryl or aryl substitutedby one to three R¹⁴, which may be the same or different, heteroaryl orheteroaryl substituted by one to three R¹⁴, which may be the same ordifferent, aryl-C₁-C₄alkyl or aryl-C₁-C₄alkyl wherein the aryl moiety issubstituted by one to three R¹⁴, which may be the same or different,heteroaryl-C₁-C₄alkyl or heteroaryl-C₁-C₄alkyl wherein the heteroarylmoiety is substituted by one to three R¹⁴, which may be the same ordifferent, aryloxy or aryloxy substituted by one to three R¹⁴, which maybe the same or different, heteroaryloxy or heteroaryloxy substituted byone to three R¹⁴, which may be the same or different, arylthio orarylthio substituted by one to three R¹⁴, which may be the same ordifferent, or heteroarylthio or heteroarylthio substituted by one tothree R¹⁴, which may be the same or different.

Most preferably R¹⁰ is iso-propyl or tert-butyl.

Preferably each R¹¹ is independently C₁-C₄alkyl.

Preferably R¹² is C₁-C₄alkyl or C₁-C₄haloalkyl.

Preferably each R¹³ is independently halo, nitro, C₁-C₄alkyl,C₁-C₄haloalkyl or C₁-C₄alkoxy. Examples of such preferred groups arechloro, fluoro, nitro, methyl, ethyl, trifluoromethyl and methoxy.

Preferably each R¹⁴ is independently halo, nitro, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy. Examples of suchpreferred groups are chloro, fluoro, nitro, methyl, ethyl,trifluoromethyl, methoxy and trifluoromethoxy.

In one embodiment the invention provides a method of controlling plantswhich comprises applying to the plants or to the locus thereof aherbicidally effective amount of a compound of formula (Ix)

wherein A¹, A², A³, A⁴, R⁴ and R⁵ are as defined for a compound offormula (I) and R³ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl,C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkyl-C₁-C₆alkyl-,C₁-C₁₀alkoxy-C₁-C₆alkyl-, C₁-C₁₀cyanoalkyl-,C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; or a salt orN-oxide thereof. The preferences for A¹, A², A³, A⁴, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are the same as the preferences set outfor the corresponding substituents of a compound of formula (I). Thepreferences for R³ are the same as the preferences set out for thecorresponding substituents of a compound of formula (I) except that R³cannot be hydrogen.

In another embodiment the invention provides a method of controllingplants which comprises applying to the plants or to the locus thereof aherbicidally effective amount of a compound of formula (Ic)

wherein A¹, A², A³, A⁴ and are as defined for a compound of formula (I)and R³ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₆alkyl-, C₁-C₁₀alkoxy-C₁-C₆alkyl-,C₁-C₁₀cyanoalkyl-, C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; and R⁵ is agroup which can be metabolised to a hydroxy group; or a salt or N-oxidethereof. The preferences for A¹, A², A³, A⁴, R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³ and R¹⁴ are the same as the preferences set out for thecorresponding substituents of a compound of formula (I). The preferencesfor R³ are the same as the preferences set out for the correspondingsubstituents of a compound of formula (I) except that R³ cannot behydrogen. The preferences for R⁵ are the same as the preferences set outfor the corresponding substituents of a compound of formula (I) exceptthat R⁵ cannot be hydroxy.

In another embodiment the invention provides a method of controllingplants which comprises applying to the plants or to the locus thereof aherbicidally effective amount of a compound of formula (Id)

wherein A¹, A², A³, A⁴ and R⁴ are as defined for a compound of formula(I) and R³ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl,C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkyl-C₁-C₆alkyl-,C₁-C₁₀alkoxy-C₁-C₆alkyl-, C₁-C₁₀cyanoalkyl-,C₁-C₁₀alkoxylcarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; or a salt orN-oxide thereof. The preferences for A¹, A², A³, A⁴, R⁴, R⁶, R⁷, R⁸ andR¹³ are the same as the preferences set out for the correspondingsubstituents of a compound of formula (I). The preferences for R³ arethe same as the preferences set out for the corresponding substituentsof a compound of formula (I) except that R³ cannot be hydrogen.

Certain compounds of formula (I) are novel and as such form a furtheraspect of the invention. One group of novel compounds are compounds offormula (Ib)

wherein A¹, A², A³, A⁴ and R⁴ are as defined for compounds of formula(I) and R⁵ is a group which can be metabolised to a hydroxy group; or asalt or N-oxide thereof. The preferences for A¹, A², A³, A⁴, R¹, R⁴, R⁶,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are the same as the preferences setout for the corresponding substituents of compounds of the formula (I).The preferences for R⁵ are the same as the preferences set out for thecorresponding substituents of compounds of formula (I) except that R⁵cannot be hydroxy.

Another group of novel compounds are compounds of formula (Ic)

wherein A¹, A², A³, A⁴ and R⁴ are as defined for a compound of formula(I) and R³ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl,C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkyl-C₁-C₆alkyl-,C₁-C₁₀alkoxy-C₁-C₆alkyl-, C₁-C₁₀cyanoalkyl-,C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-, N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; and R⁵ is agroup which can be metabolised to a hydroxy group; or a salt or N-oxidethereof; provided that the compound is not2-[4-(acetyloxy)-1,2-dihydro-2-oxo-1-phenyl-1,8-naphthyridin-3-yl]-1-methyl-pyridinium(CAS RN 115892-38-1). The preferences for A¹, A², A³, A⁴, R¹, R⁴, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are the same as the preferencesset out for the corresponding substituents of a compound of formula (I).The preferences for R³ are the same as the preferences set out for thecorresponding substituents of a compound of formula (I) except that R³cannot be hydrogen. The preferences for R⁵ are the same as thepreferences set out for the corresponding substituents of a compound offormula (I) except that R⁵ cannot be hydroxy.

A further group of novel compounds are compounds of formula (Id)

wherein A¹, A², A³, A⁴ and R⁴ are as defined for a compound of formula(I) and R³ is C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₆alkyl-, C₁-C₁₀cyanoalkyl-,C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; or a salt orN-oxide thereof; provided that the compound is not4-hydroxy-1-methyl-3-(2,4,6-trimethylphenyl)-1,8-naphthyridin-2(1H)-one(CAS RN 380634-13-9),6-chloro-4-hydroxy-1-methyl-3-(thien-3-yl)-1,8-naphthyridin-2(1H)-one(CAS RN 174347-23-0),6-chloro-4-hydroxy-1-methyl-3-(thien-3-yl)-1,8-naphthyridin-2(1H)-onesodium salt (CAS RN 174347-24-1), or6-chloro-1-ethyl-4-hydroxy-3-(thien-3-yl)-1,8-naphthyridin-2(1H)-one.The preferences for A¹, A², A³, A⁴, R¹, R⁴, R⁶, R⁷, R⁸ and R¹³ are thesame as the preferences set out for the corresponding substituents of acompound of formula (I). The preferences for R³ are the same as thepreferences set out for the corresponding substituents of a compound offormula (I) except that R³ cannot be hydrogen.

The compounds in Tables 1 to 41 below illustrate the compounds of theinvention.

TABLE 1   Table 1 provides 70 compounds of formula (I′), where R⁴ is2,5-bis-(trifluoromethyl)-   phenyl, and R³ and R⁵ have the valueslisted in Table 1. (I′)

Compound number R³ R⁵ 1.001 H —OH 1.002 H —OCOCH₃ 1.003 H —OCOCH₂CH₃1.004 H —OCOCH(CH₃)₂ 1.005 H —OCO(CH₂)₂CH₃ 1.006 H —OCOCH(CH₃)CH₂CH₃1.007 H —OCOCH₂CH(CH₃)₂ 1.008 H —OCOC(CH₃)₃ 1.009 H —O(CO)OCH₂CH₃ 1.010H —O(CO)SCH₂CH₃ 1.011 —CH₃ —OH 1.012 —CH₃ —OCOCH₃ 1.013 —CH₃ —OCOCH₂CH₃1.014 —CH₃ —OCOCH(CH₃)₂ 1.015 —CH₃ —OCO(CH₂)₂CH₃ 1.016 —CH₃—OCOCH(CH₃)CH₂CH₃ 1.017 —CH₃ —OCOCH₂CH(CH₃)₂ 1.018 —CH₃ —OCOC(CH₃)₃1.019 —CH₃ —O(CO)OCH₂CH₃ 1.020 —CH₃ —O(CO)SCH₂CH₃ 1.021 —CH₂CH₃ —OH1.022 —CH₂CH₃ —OCOCH₃ 1.023 —CH₂CH₃ —OCOCH₂CH₃ 1.024 —CH₂CH₃—OCOCH(CH₃)₂ 1.025 —CH₂CH₃ —OCO(CH₂)₂CH₃ 1.026 —CH₂CH₃ —OCOCH(CH₃)CH₂CH₃1.027 —CH₂CH₃ —OCOCH₂CH(CH₃)₂ 1.028 —CH₂CH₃ —OCOC(CH₃)₃ 1.029 —CH₂CH₃—O(CO)OCH₂CH₃ 1.030 —CH₂CH₃ —O(CO)SCH₂CH₃ 1.031 —CH₂CHF₂ —OH 1.032—CH₂CHF₂ —OCOCH₃ 1.033 —CH₂CHF₂ —OCOCH₂CH₃ 1.034 —CH₂CHF₂ —OCOCH(CH₃)₂1.035 —CH₂CHF₂ —OCO(CH₂)₂CH₃ 1.036 —CH₂CHF₂ —OCOCH(CH₃)CH₂CH₃ 1.037—CH₂CHF₂ —OCOCH₂CH(CH₃)₂ 1.038 —CH₂CHF₂ —OCOC(CH₃)₃ 1.039 —CH₂CHF₂—O(CO)OCH₂CH₃ 1.040 —CH₂CHF₂ —O(CO)SCH₂CH₃ 1.041 —CH₂CF₃ —OH 1.042—CH₂CF₃ —OCOCH₃ 1.043 —CH₂CF₃ —OCOCH₂CH₃ 1.044 —CH₂CF₃ —OCOCH(CH₃)₂1.045 —CH₂CF₃ —OCO(CH₂)₂CH₃ 1.046 —CH₂CF₃ —OCOCH(CH₃)CH₂CH₃ 1.047—CH₂CF₃ —OCOCH₂CH(CH₃)₂ 1.048 —CH₂CF₃ —OCOC(CH₃)₃ 1.049 —CH₂CF₃—O(CO)OCH₂CH₃ 1.050 —CH₂CF₃ —O(CO)SCH₂CH₃ 1.051 —CH₂CH═CH₂ —OH 1.052—CH₂CH═CH₂ —OCOCH₃ 1.053 —CH₂CH═CH₂ —OCOCH₂CH₃ 1.054 —CH₂CH═CH₂—OCOCH(CH₃)₂ 1.055 —CH₂CH═CH₂ —OCO(CH₂)₂CH₃ 1.056 —CH₂CH═CH₂—OCOCH(CH₃)CH₂CH₃ 1.057 —CH₂CH═CH₂ —OCOCH₂CH(CH₃)₂ 1.058 —CH₂CH═CH₂—OCOC(CH₃)₃ 1.059 —CH₂CH═CH₂ —O(CO)OCH₂CH₃ 1.060 —CH₂CH═CH₂—O(CO)SCH₂CH₃ 1.061 —CH₂C≡CH —OH 1.062 —CH₂C≡CH —OCOCH₃ 1.063 —CH₂C≡CH—OCOCH₂CH₃ 1.064 —CH₂C≡CH —OCOCH(CH₃)₂ 1.065 —CH₂C≡CH —OCO(CH₂)₂CH₃1.066 —CH₂C≡CH —OCOCH(CH₃)CH₂CH₃ 1.067 —CH₂C≡CH —OCOCH₂CH(CH₃)₂ 1.068—CH₂C≡CH —OCOC(CH₃)₃ 1.069 —CH₂C≡CH —O(CO)OCH₂CH₃ 1.070 —CH₂C≡CH—O(CO)SCH₂CH₃

Table 2:

Table 2 provides 70 compounds of formula (I′), where R⁴ is3-bromo-2-chloro-6-fluoro-phenyl, and R³ and R⁵ have the values listedin Table 1.

Table 3:

Table 3 provides 70 compounds of formula (I′), where R⁴ is2-chloro-3,6-difluoro-phenyl, and R³ and R⁵ have the values listed inTable 1.

Table 4:

Table 4 provides 70 compounds of formula (I′), where R⁴ is2-chloro-4-fluoro-phenyl, and R³ and R⁵ have the values listed in Table1.

Table 5:

Table 5 provides 70 compounds of formula (I′), where R⁴ is2-chloro-5-fluoro-phenyl, and R³ and R⁵ have the values listed in Table1.

Table 6:

Table 6 provides 70 compounds of formula (I′), where R⁴ is2-chloro-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 7:

Table 7 provides 70 compounds of formula (I′), where R⁴ is2-chloro-3-trifluoromethyl-phenyl, and R³ and R⁵ have the values listedin Table 1.

Table 8:

Table 8 provides 70 compounds of formula (I′), where R⁴ is2-chloro-5-trifluoromethyl-phenyl, and R³ and R⁵ have the values listedin Table 1.

Table 9:

Table 9 provides 70 compounds of formula (I′), where R⁴ is2-chloro-6-trifluoromethyl-phenyl, and R³ and R⁵ have the values listedin Table 1.

Table 10:

Table 10 provides 70 compounds of formula (I′), where R⁴ is2,3-dichloro-6-fluoro-phenyl, and R³ and R⁵ have the values listed inTable 1.

Table 11:

Table 11 provides 70 compounds of formula (I′), where R⁴ is2,4-dichloro-5-fluoro-phenyl, and R³ and R⁵ have the values listed inTable 1.

Table 12:

Table 12 provides 70 compounds of formula (I′), where R⁴ is3,5-dichloro-2-methoxy-phenyl, and R³ and R⁵ have the values listed inTable 1.

Table 13:

Table 13 provides 70 compounds of formula (I′), where R⁴ is2,3-dichloro-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 14:

Table 14 provides 70 compounds of formula (I′), where R⁴ is2,4-dichloro-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 15:

Table 15 provides 70 compounds of formula (I′), where R⁴ is2,5-dichloro-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 16:

Table 16 provides 70 compounds of formula (I′), where R⁴ is2,6-dichloro-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 17:

Table 17 provides 70 compounds of formula (I′), where R⁴ is2,6-dichloro-4-trifluoro-methoxy-phenyl, and R³ and R⁵ have the valueslisted in Table 1.

Table 18:

Table 18 provides 70 compounds of formula (I′), where R⁴ is2,6-dichloro-4-trifluoro-methyl-phenyl, and R³ and R⁵ have the valueslisted in Table 1.

Table 19:

Table 19 provides 70 compounds of formula (I′), where R⁴ is2,6-diethyl-4-methyl-phenyl, and R³ and R⁵ have the values listed inTable 1.

Table 20:

Table 20 provides 70 compounds of formula (I′), where R⁴ is2,3-dimethoxy-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 21:

Table 21 provides 70 compounds of formula (I′), where R⁴ is2-methoxy-5-trifluoro-methoxy-phenyl, and R³ and R⁵ have the valueslisted in Table 1.

Table 22:

Table 22 provides 70 compounds of formula (I′), where R⁴ is2,3,6-trichloro-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 23:

Table 23 provides 70 compounds of formula (I′), where R⁴ is2-trifluoromethoxy-phenyl, and R³ and R⁵ have the values listed in Table1.

Table 24:

Table 24 provides 70 compounds of formula (I′), where R⁴ is2-trifluoromethyl-phenyl, and R³ and R⁵ have the values listed in Table1.

Table 25:

Table 25 provides 70 compounds of formula (I′), where R⁴ is2,4,6-trimethyl-phenyl, and R³ and R⁵ have the values listed in Table 1.

Table 26:

Table 26 provides 70 compounds of formula (I′), where R⁴ is3,5-dichloro-pyrid-2-yl, and R³ and R⁵ have the values listed in Table1.

Table 27:

Table 27 provides 70 compounds of formula (I′), where R⁴ is3,5-dichloro-pyrid-4-yl, and R³ and R⁵ have the values listed in Table1.

Table 28:

Table 28 provides 70 compounds of formula (I′), where R⁴ is2,6-dichloro-pyrid-3-yl, and R³ and R⁵ have the values listed in Table1.

Table 29:

Table 29 provides 70 compounds of formula (0, where R⁴ is2,4-dichloro-pyrid-3-yl, and R³ and R⁵ have the values listed in Table1.

Table 30:

Table 30 provides 70 compounds of formula (I′), where R⁴ is4,6-dichloro-pyrid-3-yl, and R³ and R⁵ have the values listed in Table1.

Table 31:

Table 31 provides 70 compounds of formula (I′), where R⁴ is2,5-dichloro-pyrid-4-yl, and R³ and R⁵ have the values listed in Table1.

Table 32:

Table 32 provides 70 compounds of formula (I′), where R⁴ is3,6-dichloro-pyrid-2-yl, and R³ and R⁵ have the values listed in Table1.

Table 33:

Table 33 provides 70 compounds of formula (I′), where R⁴ is3-chloro-5-fluoro-pyrid-2-yl, and R³ and R⁵ have the values listed inTable 1.

Table 34:

Table 34 provides 70 compounds of formula (I′), where R⁴ is3-chloro-5-trifluoromethyl-pyrid-2-yl, and R³ and R⁵ have the valueslisted in Table 1.

Table 35:

Table 35 provides 70 compounds of formula (I′), where R⁴ is3,5,6-trichloro-pyrid-2-yl, and R³ and R⁵ have the values listed inTable 1.

Table 36:

Table 36 provides 70 compounds of formula (I′), where R⁴ is3,5-dichloro-pyrid-3-yl, and R³ and R⁵ have the values listed in Table1.

Table 37:

Table 37 provides 70 compounds of formula (I′), where R⁴ is2,3-dichloro-pyrid-4-yl, and R³ and R⁵ have the values listed in Table1.

Table 38:

Table 38 provides 70 compounds of formula (I′), where R⁴ is2-chloro-4-trifluoromethyl-pyrid-3-yl, and R³ and R⁵ have the valueslisted in Table 1.

Table 39:

Table 39 provides 70 compounds of formula (I′), where R⁴ is2-chloro-6-trifluoromethyl-pyrid-3-yl, and R³ and R⁵ have the valueslisted in Table 1.

Table 40:

Table 40 provides 70 compounds of formula (I), where R⁴ is3-chloro-5-trifluoromethyl-pyrid-4-yl, and R³ and R⁵ have the valueslisted in Table 1.

Table 41:

Table 41 provides 70 compounds of formula (I′), where R⁴ is2,3,5-trichloro-pyrid-4-yl, and R³ and R⁵ have the values listed inTable 1.

The compounds of the invention may be made by a variety of methods, forexample by the methods described in Schemes 1 to 4.

1) Compounds of formula (3) as shown in Scheme 1 wherein A¹, A², A³ andA⁴ are as defined for a compound of formula (I) and R¹⁶ is C₁-C₆alkylcan be made by reaction of an aminopyrazine acid of formula (2) whereinA¹, A², A³, A⁴ are as defined for a compound of formula (I) via methodsknown to the person skilled in the art. For example, the transformationof an aminopyrazine acid to its methyl ester can conveniently be carriedout in a suitable solvent mixture, such as methanol and toluene, using(trimethylsilyl)diazomethane as reagent.

2) Compounds of formula (5) wherein A¹, A², A³, A⁴ and R⁴ are as definedfor a compound of formula (I) and R¹⁶ is C₁-C₆alkyl can be made byreaction of an amino-pyrazine ester of formula (3) as defined in 1)wherein A¹, A², A³ and A⁴ are as defined for a compound of formula (I)and R¹⁶ is C₁-C₆alkyl with an acid derivative of formula (4) wherein R⁴is as defined for a compound of formula (I) and X is halogen or hydroxy.For example, if (4) is an acid chloride (i.e. where X is chlorine) thereaction can conveniently be carried out optionally in the presence of abase, such as triethylamine or pyridine, in a suitable solvent, such asacetonitrile or dichloromethane, optionally using microwave heating.Alternatively, if (4) is a carboxylic acid (i.e. where X is hydroxy) thereaction can conveniently be carried out using an amide coupling method,for example by reaction with a coupling agent, such asbis(2-oxo-3-oxazolidinyl)phosphinic chloride orN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (“EDAC”),in the presence of a base, such as triethylamine, in a suitable solvent,such as dichloromethane, or other amide coupling methods which have beenreviewed in Tetrahedron (2005), 61(46), 10827-10852.

3) Compounds of formula (Ia) wherein A¹, A², A³, A⁴ and R⁴ are asdefined for a compound of formula (I) can be prepared by treating acompound of formula (5) as defined in 2) with a base in a suitablesolvent, such as potassium carbonate in N,N-dimethylformamide or lithiumhexamethyldisilazide in tetrahydrofuran, optionally using microwaveheating.

4) Alternatively, where R⁴ is heterocyclic and where (4) is a carboxylicester (i.e. where X is OR¹⁶ and R¹⁶ is as defined in 1), the compoundsof formula (Ia) as defined in 3) can also be prepared directly byreaction of a compound of formula (3) as defined in 1) with ancarboxylic ester of formula (4) as defined here in the presence of abase, such as sodium ethoxide, in a suitable solvent, such asN,N-dimethylformamide, optionally using microwave heating.

5) Compounds of formula (Ie) wherein A¹, A², A³, A⁴, R⁴ and R¹⁰ are asdefined for a compound of formula (I) can be prepared by reaction of acompound of formula (Ia) as defined in 3) with an acid chloride offormula R¹⁰COCl or an acid anhydride of formula (R¹⁰CO)₂O wherein R¹⁰ isas defined for a compound of formula (I), optionally in the presence ofa base, such as triethylamine or pyridine, optionally in a suitablesolvent, such as dichloromethane, optionally using microwave heating.

6) Compounds of formula (Id) wherein A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I), with R³ other than hydrogen, canbe prepared by treating a compound of formula (Ie) as defined in 5) byreaction with a compound of formula R³LG wherein R³ is as defined for acompound of formula (I) and LG is a leaving group such as a halide, forexample bromide or iodide, or tosylate, mesylate or triflate, in thepresence of a base, such as potassium carbonate, optionally in thepresence of an activator/iodide, such as potassium iodide, in a suitablesolvent, such as acetonitrile or N,N-dimethylformamide, optionally usingmicrowave heating, as shown in Scheme 2.

7) Compounds of formula (If) wherein A¹, A², A³, A⁴, R³, R⁴ and R¹⁰ areas defined for a compound of formula (I), with R³ other than hydrogen,can be prepared by reaction of a compound of formula (Id) as defined in6) with an acid chloride of formula R¹⁰COCl or an acid anhydride offormula (R¹⁰CO)₂O wherein R¹⁰ is as defined for a compound of formula(I), optionally in the presence of a base, such as potassiumtert-butoxide or pyridine, optionally in a suitable solvent, such asdichloromethane or tetrahydrofuran, optionally using microwave heating.

8) Compounds of formula (6) wherein A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I), with R³ other than hydrogen, andR¹⁶ is as defined in 1) can be prepared by treating a compound offormula (5) as defined in 2) by reaction with a compound of formula R³LGas defined in 6), in the presence of a base, such as sodium hydride, ina suitable solvent, such as N,N-dimethylformamide, optionally usingmicrowave heating, as shown in Scheme 3.

9) Compounds of formula (Id) as defined in 6), can be prepared bytreating a compound of formula (6) as defined in 8) with a base, such aspotassium tert-butoxide or lithium hexamethyldisilazide, in a suitablesolvent, such as N,N-dimethylformamide or tetrahydrofuran, optionallyusing microwave heating.

10) Compounds of formula (If) as defined in 7), can be prepared in a onepot procedure by treating a compound of formula (6) as defined in 8)with a base, such as sodium hexamethyldisilazide, in a suitable solvent,such as tetrahydrofuran, followed by an acid chloride of formula R¹⁰COClor an acid anhydride of formula (R¹⁰CO)₂O wherein R¹⁰ is as defined fora compound of formula (I).

11) Compounds of formula (8) wherein A¹, A², A³, A⁴ and R³ are asdefined for a compound of formula (I), with R³ other than hydrogen, andR¹⁶ is as defined in 1) can be prepared from a compound of formula (7)wherein A¹, A², A³ and A⁴ are as defined for a compound of formula (I)and R¹⁶ is as defined in 1) by reaction with an amine of formula R³NH₂wherein R³ is as defined for a compound of formula (I) in the presenceof a base, such as diisopropylethylamine, in a suitable solvent, such asethanol, optionally using microwave heating, as shown in Scheme 4.

12) Compounds of formula (6) as defined in 8), can be prepared bytreating a compound of formula (8) as defined in 11) with an acidderivative of formula (4) as defined in 2).

The compounds of formula (I) according to the invention can be used asherbicides in unmodified form, as obtained in the synthesis, but theyare generally formulated into herbicidal compositions in various waysusing formulation adjuvants, such as carriers, solvents andsurface-active substances. The formulations can be in various physicalforms, e.g. in the form of dusting powders, gels, wettable powders,water-dispersible granules, water-dispersible tablets, effervescentpellets, emulsifiable concentrates, microemulsifiable concentrates,oil-in-water emulsions, oil-flowables, aqueous dispersions, oilydispersions, suspo-emulsions, capsule suspensions, emulsifiablegranules, soluble liquids, water-soluble concentrates (with water or awater-miscible organic solvent as carrier), impregnated polymer films orin other forms known e.g. from the Manual on Development and Use of FAOSpecifications for Plant Protection Products, 5th Edition, 1999. Suchformulations can either be used directly or they are diluted prior touse. The dilutions can be made, for example, with water, liquidfertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof. The active ingredients can also be contained in very finemicrocapsules consisting of a polymer. Microcapsules contain the activeingredients in a porous carrier. This enables the active ingredients tobe released into the environment in controlled amounts (e.g.slow-release). Microcapsules usually have diameter of from 0.1 to 500microns. They contain active ingredients in an amount of about from 25to 95% by weight of the capsule weight. The active ingredients can be inthe form of a monolithic solid, in the form of fine particles in solidor liquid dispersion or in the form of a suitable solution. Theencapsulating membranes comprise, for example, natural or syntheticrubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile,polyacrylate, polyesters, polyamides, polyureas, polyurethane orchemically modified polymers and starch xanthates or other polymers thatare known to the person skilled in the art in this connection.Alternatively, very fine microcapsules can be formed in which the activeingredient is contained in the form of finely divided particles in asolid matrix of base substance, but the microcapsules are not themselvesencapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octa-decanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400),propionic acid, propyl lactate, propylene carbonate, propylene glycol,propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate,triethylene glycol, xylenesulfonic acid, paraffin, mineral oil,trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butylacetate, propylene glycol methyl ether, diethylene glycol methyl ether,methanol, ethanol, isopropanol, and alcohols of higher molecular weight,such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol,ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone andthe like. Water is generally the carrier of choice for diluting theconcentrates. Suitable solid carriers are, for example, talc, titaniumdioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr,limestone, calcium carbonate, bentonite, calcium montmorillonite,cottonseed husks, wheat flour, soybean flour, pumice, wood flour, groundwalnut shells, lignin and similar substances, as described, for example,in CFR 180.1001. (c) & (d).

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono- and di-alkylphosphate esters; and also further substancesdescribed e.g. in “McCutcheon's Detergents and Emulsifiers Annual” MCPublishing Corp., Ridgewood N.J., 1981.

Further adjuvants that can usually be used in pesticidal formulationsinclude crystallisation inhibitors, viscosity modifiers, suspendingagents, dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, and alsoliquid and solid fertilisers.

The compositions according to the invention can additionally include anadditive comprising an oil of vegetable or animal origin, a mineral oil,alkyl esters of such oils or mixtures of such oils and oil derivatives.The amount of oil additive in the composition according to the inventionis generally from 0.01 to 10%, based on the spray mixture. For example,the oil additive can be added to the spray tank in the desiredconcentration after the spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils ofvegetable origin, for example the methyl derivatives, or an oil ofanimal origin, such as fish oil or beef tallow. A preferred additivecontains, for example, as active components essentially 80% by weightalkyl esters of fish oils and 15% by weight methylated rapeseed oil, andalso 5% by weight of customary emulsifiers and pH modifiers. Especiallypreferred oil additives comprise alkyl esters of C₈-C₂₂ fatty acids,especially the methyl derivatives of C₁₂-C₁₈ fatty acids, for examplethe methyl esters of lauric acid, palmitic acid and oleic acid, being ofimportance. Those esters are known as methyl laurate (CAS-111-82-0),methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). Apreferred fatty acid methyl ester derivative is Emery® 2230 and 2231(Cognis GmbH). Those and other oil derivatives are also known from theCompendium of Herbicide Adjuvants, 5th Edition, Southern IllinoisUniversity, 2000.

The application and action of the oil additives can be further improvedby combination with surface-active substances, such as non-ionic,anionic or cationic surfactants. Examples of suitable anionic, non-ionicand cationic surfactants are listed on pages 7 and 8 of WO 97/34485.Preferred surface-active substances are anionic surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof, andalso non-ionic surfactants of the fatty alcohol ethoxylate type. Specialpreference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having adegree of ethoxylation of from 5 to 40. Examples of commerciallyavailable surfactants are the Genapol types (Clariant AG). Alsopreferred are silicone surfactants, especially polyalkyl-oxide-modifiedheptamethyltriloxanes which are commercially available e.g. as SilwetL-77®, and also perfluorinated surfactants. The concentration of thesurface-active substances in relation to the total additive is generallyfrom 1 to 30% by weight. Examples of oil additives consisting ofmixtures of oil or mineral oils or derivatives thereof with surfactantsare Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP OilUK Limited, GB).

If desired, it is also possible for the mentioned surface-activesubstances to be used in the formulations on their own, that is to saywithout oil additives.

Furthermore, the addition of an organic solvent to the oiladditive/surfactant mixture may contribute to an additional enhancementof action. Suitable solvents are, for example, Solvesso® (ESSO) orAromatic Solvent® (Exxon Corporation). The concentration of suchsolvents can be from 10 to 80% by weight of the total weight. Oiladditives that are present in admixture with solvents are described, forexample, in U.S. Pat. No. 4,834,908. A commercially available oiladditive disclosed therein is known by the name MERGE® (BASFCorporation). A further oil additive that is preferred according to theinvention is SCORE® (Syngenta Crop Protection Canada).

In addition to the oil additives listed above, for the purpose ofenhancing the action of the compositions according to the invention itis also possible for formulations of alkylpyrrolidones (e.g. Agrimax®)to be added to the spray mixture. Formulations of synthetic lattices,e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g.Bond®, Courier® or Emerald®) may also be used. It is also possible forsolutions that contain propionic acid, for example EurogkemPen-e-trate®, to be added to the spray mixture as action-enhancingagent.

The herbicidal compositions generally comprise from 0.1 to 99% byweight, especially from 0.1 to 95% by weight, compounds of formula (I)and from 1 to 99.9% by weight of a formulation adjuvant which preferablyincludes from 0 to 25% by weight of a surface-active substance. Whereascommercial products will preferably be formulated as concentrates, theend user will normally employ dilute formulations.

The rates of application of compounds of formula (I) may vary withinwide limits and depend on the nature of the soil, the method ofapplication (pre- or post-emergence; seed dressing; application to theseed furrow; no tillage application etc.), the crop plant, the grass orweed to be controlled, the prevailing climatic conditions, and otherfactors governed by the method of application, the time of applicationand the target crop. The compounds of formula (I) according to theinvention are generally applied at a rate of from 10 to 2000 g/ha,especially from 50 to 1000 g/ha.

Preferred formulations have especially the following compositions(%=percent by weight):

Emulsifiable Concentrates:

-   active ingredient: 1 to 95%, preferably 60 to 90%-   surface-active agent: 1 to 30%, preferably 5 to 20%-   liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

-   active ingredient: 0.1 to 10%, preferably 0.1 to 5%-   solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

-   active ingredient: 5 to 75%, preferably 10 to 50%-   water: 94 to 24%, preferably 88 to 30%-   surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

-   active ingredient: 0.5 to 90%, preferably 1 to 80%-   surface-active agent: 0.5 to 20%, preferably 1 to 15%-   solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

-   active ingredient: 0.1 to 30%, preferably 0.1 to 15%-   solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Formulation Examples for herbicides of formula (I) (%=% by weight)

F1. Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25%50% calcium dodecylbenzenesulfonate 6%  8%  6%  8% castor oil polyglycolether 4% —  4%  4% (36 mol of ethylene oxide) octylphenol polyglycolether —  4% —  2% (7-8 mol of ethylene oxide) NMP — — 10% 20% arom.hydrocarbon mixture 85%  78% 55% 16% C₉-C₁₂

Emulsions of any desired concentration can be obtained from suchconcentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient  5% 10% 50% 90%1-methoxy-3-(3-methoxy- propoxy)-propane — 20% 20% — polyethylene glycolMW 400 20% 10% — — NMP — — 30% 10% arom. hydrocarbon mixture 75% 60% — —C₉-C₁₂

The solutions are suitable for use in the form of microdrops.

F3. Wettable powders a) b) c) d) active ingredient 5% 25%  50%  80%sodium lignosulfonate 4% — 3% — sodium lauryl sulfate 2% 3% —  4% sodiumdiisobutylnaphthalene- sulfonate — 6% 5%  6% octylphenol polyglycolether — 1% 2% — (7-8 mol of ethylene oxide) highly dispersed silicicacid 1% 3% 5% 10% kaolin 88%  62%  35%  —

The active ingredient is mixed thoroughly with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of anydesired concentration.

F4. Coated granules a) b) c) active ingredient 0.1% 5% 15% highlydispersed silicic acid 0.9% 2%  2% inorganic carrier 99.0% 93%  83%(diameter 0.1-1 mm) e.g. CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride and applied tothe carrier by spraying, and the solvent is then evaporated off invacuo.

F5. Coated granules a) b) c) active ingredient 0.1% 5% 15% polyethyleneglycol MW 200 1.0% 2%  3% highly dispersed silicic acid 0.9% 1%  2%inorganic carrier 98.0% 92%  80% (diameter 0.1 - 1 mm) e.g. CaCO₃ orSiO₂

The finely ground active ingredient is uniformly applied, in a mixer, tothe carrier moistened with polyethylene glycol. Non-dusty coatedgranules are obtained in this manner.

F6. Extruder granules a) b) c) d) active ingredient 0.1% 3% 5% 15%sodium lignosulfonate 1.5% 2% 3%  4% carboxymethylcellulose 1.4% 2% 2% 2% kaolin 97.0% 93%  90%  79%

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

F7. Dusts a) b) c) active ingredient 0.1%  1%  5% talcum 39.9% 49% 35%kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with thecarriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient 3% 10%  25% 50%  ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether — 1% 2% —(15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5%carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2%  0.2% 0.2%  0.2%  solution silicone oil emulsion 0.8%  0.8%  0.8%  0.8%  water87% 79%  62%  38% 

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

The invention relates to a method of controlling plants which comprisesapplying to the plants or to the locus thereof a herbicidally effectiveamount of a compound of formula (I).

The invention also relates to a method of inhibiting plant growth whichcomprises applying to the plants or to the locus thereof a herbicidallyeffective amount of a compound of formula (I).

The invention also relates to a method of selectively controllinggrasses and weeds in crops of useful plants which comprises applying tothe useful plants or locus thereof or to the area of cultivation aherbicidally effective amount of a compound of formula (I).

Crops of useful plants in which the composition according to theinvention can be used include perennial crops, such as citrus fruit,grapevines, nuts, oil palms, olives, pome fruit, stone fruit and rubber,and annual arable crops, such as cereals, for example barley and wheat,cotton, oilseed rape, maize, rice, soy beans, sugar beet, sugar cane,sunflowers, ornamentals and vegetables, especially cereals, maize andsoy beans.

The grasses and weeds to be controlled may be both mono-cotyledonousspecies, for example Agrostis, Alopecurus, Avena, Bromus, Cyperus,Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria,Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, forexample Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium,Ipomoea, Nasturtium, Sinapis, Solanum, Stellaria, Veronica, Viola andXanthium.

Crops are to be understood as also including those crops which have beenrendered tolerant to herbicides or classes of herbicides (e.g. auxins orALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods ofbreeding or by genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding is Clearfield® summer rape (canola). Examples ofcrops that have been rendered tolerant to herbicides by geneticengineering methods include e.g. glyphosate- and glufosinate-resistantmaize varieties commercially available under the trade namesRoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt 176 maize hybrids of NK® (SyngentaSeeds). The Bt toxin is a protein that is formed naturally by Bacillusthuringiensis soil bacteria. Examples of toxins, or transgenic plantsable to synthesize such toxins, are described in EP-A-451 878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examplesof transgenic plants comprising one or more genes that code for aninsecticidal resistance and express one or more toxins are KnockOut®(maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton),NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seedmaterial thereof can be both resistant to herbicides and, at the sametime, resistant to insect feeding (“stacked” transgenic events). Forexample, seed can have the ability to express an insecticidal Cry3protein while at the same time being tolerant to glyphosate.

Crops are also to be understood as being those which are obtained byconventional methods of breeding or genetic engineering and containso-called output traits (e.g. improved storage stability, highernutritional value and improved flavor).

Areas under cultivation include land on which the crop plants arealready growing and land intended for cultivation with those cropplants. The compounds of the invention can be applied before weedsemerge (pre-emergence application) or after weeds emerge (post-emergenceapplication), and are particularly effective when appliedpost-emergence.

The compounds of formula (I) according to the invention can also be usedin combination with one or more further herbicides. In particular, thefollowing mixtures of the compound of formula (I) are important:

Mixtures of a compound of formula (I) with a synthetic auxin (e.g.compound of formula (I)+clopyralid (162), compound of formula (I)+2,4-D(211), compound of formula (I)+dicamba (228), compound of formula(I)+diphenamid (274), compound of formula (I)+MCPA (499), compound offormula (I)+quinclorac (712), or compound of formula (I)+aminopyralid(CAS RN 150114-71-9)).

Mixtures of a compound of formula (I) with diflufenzopyr (252).

Mixtures of a compound of formula (I) with an acetanilide (e.g. compoundof formula (I)+acetochlor (5), compound of formula (I)+dimethenamid(260), compound of formula (I)+metolachlor (548), compound of formula(I)+S-metolachlor (549), or compound of formula (I)+pretilachlor (656)).

Mixtures of a compound of formula (I) with flamprop-M (355).

Mixtures of a compound of formula (I) with flufenacet (BAY FOE 5043)(369).

Mixtures of a compound of formula (I) with pyroxasulfone (CAS RN447399-55-5).

Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g.compound of formula (I)+isoxaflutole (479), compound of formula(I)+mesotrione (515), compound of formula (I)+pyrasulfotole (CAS RN365400-11-9), compound of formula (I)+sulcotrione (747), compound offormula (I)+tembotrione (CAS RN 335104-84-2), compound of formula(I)+topramezone (CAS RN 210631-68-8), compound of formula(I)+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one(CAS RN 352010-68-5), or compound of formula(I)+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one(CAS RN 894355-80-7)).

Mixtures of a compound of formula (I) with a triazine (e.g. compound offormula (I)+atrazine (37), or compound of formula (I)+terbuthylazine(775)).

Mixtures of a compound of formula (I) with a triazine and an HPPDinhibitor (e.g. compound of formula (I)+triazine+isoxaflutole, compoundof formula (I)+triazine+mesotrione, compound of formula(I)+triazine+pyrasulfotole, compound of formula(I)+triazine+sulcotrione, compound of formula (I)+triazine+tembotrione,compound of formula (I)+triazine+topramezone, compound of formula(I)+triazine+4-hydroxy-3-[[2-[(2-methoxyethoxy)-methyl]-6-(trifluoro-methyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one,or compound of formula(I)+triazine+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoro-methyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one).

Mixtures of a compound of formula (I) with glyphosate (419).

Mixtures of a compound of formula (I) with glyphosate and an HPPDinhibitor (e.g. compound of formula (I)+glyphosate+isoxaflutole,compound of formula (I)+glyphosate+mesotrione, compound of formula(I)+glyphosate+pyrasulfotole, compound of formula(I)+glyphosate+sulcotrione, compound of formula(I)+glyphosate+tembotrione, compound of formula(I)+glyphosate+topramezone, compound of formula(I)+glyphosate+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one,or compound of formula(I)+glyphosate+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one).

Mixtures of a compound of formula (I) with glufosinate-ammonium (418).

Mixtures of a compound of formula (I) with glufosinate-ammonium and anHPPD inhibitor (e.g. compound of formula(I)+glufosinate-ammonium+isoxaflutole, compound of formula(I)+glufosinate-ammonium+mesotrione, compound of formula(I)+glufosinate-ammonium+pyrasulfotole, compound of formula(I)+glufosinate-ammonium+sulcotrione, compound of formula(I)+glufosinate-ammonium+tembotrione, compound of formula(I)+glufosinate-ammonium+topramezone, compound of formula(I)+glufosinate-ammonium+4-hydroxy-3-[[2-[(2-methoxy-ethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one,or compound of formula(I)+glufosinate-ammonium+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one).

Mixtures of a compound of formula (I) with an ALS or an AHAS inhibitor(e.g. compound of formula (I)+bensulfuron-methyl (64), compound offormula (I)+chlorimuron-ethyl (135), compound of formula(I)+cloransulam-methyl (164), compound of formula (I)+florasulam (359),compound of formula (I)+flucarbazone-sodium (364), compound of formula(I)+imazamox (451), compound of formula (I)+imazapyr (453), compound offormula (I)+imazethapyr (455), compound of formula(I)+iodosulfuron-methyl-sodium (466), compound of formula(I)+mesosulfuron-methyl (514), compound of formula (I)+nicosulfuron(577), compound of formula (I)+penoxsulam (622), compound of formula(I)+pyroxsulam (triflosulam) (CAS RN 422556-08-9), compound of formula(I)+thifensulfuron-methyl (thiameturon-methyl) (795), compound offormula (I)+triasulfuron (817), compound of formula(I)+tribenuron-methyl (822), compound of formula(I)+trifloxysulfuron-sodium (833), compound of formula(I)+thiencarbazone(4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylicacid, BAY636)), or compound of formula (I)+thiencarbazone-methyl (methyl4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylate,CAS RN 317815-83-1, BAY636-methyl)).

Mixtures of a compound of formula (I) with a PPO inhibitor (e.g.compound of formula (I)+acifluorfen-sodium (7), compound of formula(I)+butafenacil (101), compound of formula (I)+carfentrazone-ethyl(121), compound of formula (I)+cinidon-ethyl (152), compound of formula(I)+flumioxazin (376), compound of formula (I)+fomesafen (401), compoundof formula (I)+lactofen (486), or compound of formula(I)+[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]aceticacid ethyl ester) (CAS RN 353292-31-6)).

Mixtures of a compound of formula (I) with an ACCase inhibitor (e.g.compound of formula (I)+butroxydim (106), compound of formula(I)+clethodim (155), compound of formula (I)+clodinafop-propargyl (156),compound of formula (I)+cycloxydim (190), compound of formula(I)+cyhalofop-butyl (195), compound of formula (I)+diclofop-methyl(238), compound of formula (I)+fenoxaprop-P-ethyl (339), compound offormula (I)+fluazifop-butyl (361), compound of formula(I)+fluazifop-P-butyl (362), compound of formula (I)+haloxyfop (427),compound of formula (I)+haloxyfop-P (428), compound of formula(I)+propaquizafop (670), compound of formula (I)+quizalofop (717),compound of formula (I)+quizalofop-P (718), compound of formula(I)+sethoxydim (726), compound of formula (I)+tepraloxydim (771),compound of formula (I)+tralkoxydim (811)), or compound of formula(I)+pinoxaden (CAS RN 243973-20-8).

Mixtures of a compound of formula (I) with prosulfocarb (683), or acompound of formula (I) with tri-allate (816).

Mixtures of a compound of formula (I) with bromoxynil (95), a compoundof formula (I) with chloridazon (134), a compound of formula (I) withchlorotoluron (143), a compound of formula (I) with diuron (281), or acompound of formula (I) with metribuzin (554).

Mixtures of a compound of formula (I) with clomazone (159), a compoundof formula (I) with diflufenican (251), a compound of formula (I) withfluorochloridone (389), or a compound of formula (I) with flurtamone(392).

Mixtures of a compound of formula (I) with pendimethalin (621) or acompound of formula (I) with trifluralin (836).

Mixtures of a compound of formula (I) with difenzoquat metilsulfate(248).

Mixtures of a compound of formula (I) with diquat dibromide (276).

Mixtures of a compound of formula (I) with paraquat dichloride (614).

The mixing partners of the compound of formula (I) may also be in theform of esters or salts, as mentioned e.g. in The Pesticide Manual, 13thEdition (BCPC), 2003. The reference to glufosinate-ammonium also appliesto glufosinate, the reference to cloransulam-methyl also applies tocloransulam, the reference to dimethenamid also applies todimethenamid-P, the reference to flamprop-M also applies to flamprop,and the reference to pyrithiobac-sodium also applies to pyrithiobac,etc.

The mixing ratio of the compound of formula (I) to the mixing partner ispreferably from 1:100 to 1000:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula (I) with the mixing partner).

Additionally, one or more of the following herbicides or plant growthregulators can be used in combination with a compound of formula (I)according to the invention or in combination with a mixture as describedabove: aclonifen (8), acrolein (10), alachlor (14), alloxydim (18),ametryn (20), amicarbazone (21), amidosulfuron (22), aminocyclopyrachlor(CAS RN 858956-08-8), amitrole (aminotriazole) (25), ammonium sulfamate(26), anilofos (31), asulam (36), aviglycine (39), azafenidin (CAS RN68049-83-2), azimsulfuron (43), BAS 800H(CAS RN 372137-35-4),beflubutamid (55), benazolin (57), bencarbazone (CAS RN 173980-17-1),benfluralin (59), benfuresate (61), bensulide (65), bentazone (67),benzfendizone (CAS RN 158755-95-4), benzobicyclon (69), benzofenap (70),bilanafos (bialaphos) (77), bispyribac-sodium (82), borax (86), bromacil(90), bromobutide (93), bromofenoxim (CAS RN 13181-17-4), butachlor(100), butamifos (102), butralin (105), butylate (108), cafenstrole(110), carbetamide (117), chlorbromuron (CAS RN 13360-45-7),chlorflurenol-methyl (133), chloroacetic acid (138), chlorpropham (144),chlorsulfuron (147), chlorthal-dimethyl (148), cinmethylin (153),cinosulfuron (154), clomeprop (160), cumyluron (180), cyanamide (182),cyanazine (183), cyclanilide (186), cycloate (187), cyclosulfamuron(189), daimuron (213), dalapon (214), dazomet (216), desmedipham (225),desmetryn (CAS RN 1014-69-3), dichlobenil (229), dichlorprop (234),dichlorprop-P (235), diclosulam (241), dimefuron (256), dimepiperate(257), dimethachlor (258), dimethametryn (259), dimethipin (261),dimethylarsinic acid (264), dinitramine (268), dinoterb (272),dipropetryn (CAS RN 4147-51-7), dithiopyr (280), DNOC (282), DSMA (CASRN 144-21-8), endothal (295), EPTC (299), esprocarb (303), ethalfluralin(305), ethametsulfuron-methyl (306), ethephon (307), ethofumesate (311),ethoxyfen (CAS RN 188634-90-4), ethoxyfen-ethyl (CAS RN 131086-42-5),ethoxysulfuron (314), etobenzanid (318), fentrazamide (348), ferroussulfate (353), flazasulfuron (356), fluazolate (isopropazol) (CAS RN174514-07-9), flucetosulfuron (CAS RN 412928-75-7), fluchloralin (365),flufenpyr-ethyl (371), flumetralin (373), flumetsulam (374),flumiclorac-pentyl (375), flumipropyn (flumipropin) (CAS RN 84478-52-4),fluometuron (378), fluoroglycofen-ethyl (380), flupoxam (CAS RN119126-15-7), flupropacil (CAS RN 120890-70-2), flupropanate (383),flupyrsulfuron-methyl-sodium (384), flurenol (387), fluridone (388),fluoroxypyr (390), fluthiacet-methyl (395), foramsulfuron (402),fosamine (406), halosulfuron-methyl (426), HC-252 (429), hexazinone(440), imazamethabenz-methyl (450), imazapic (452), imazaquin (454),imazosulfuron (456), indanofan (462), ioxynil (467), isoproturon (475),isouron (476), isoxaben (477), isoxachlortole (CAS RN 141112-06-3),isoxapyrifop (CAS RN 87757-18-4), karbutilate (482), lenacil (487),linuron (489), MCPA-thioethyl (500), MCPB (501), mecoprop (503),mecoprop-P (504), mefenacet (505), mefluidide (507), metam (519),metamifop (mefluoxafop) (520), metamitron (521), metazachlor (524),methabenzthiazuron (526), methazole (CAS RN 20354-26-1), methylarsonicacid (536), 1-methylcyclopropene (538), methyldymron (539), methylisothiocyanate (543), metobenzuron (547), metobromuron (CAS RN3060-89-7), metosulam (552), metoxuron (553), metsulfuron-methyl (555),MK-616 (559), molinate (560), monolinuron (562), MSMA (CAS RN2163-80-6), naproanilide (571), napropamide (572), naptalam (573),neburon (574), nipyraclofen (CAS RN 99662-11-0), n-methyl-glyphosate,nonanoic acid (583), norflurazon (584), oleic acid (fatty acids) (593),orbencarb (595), orthosulfamuron (CAS RN 213464-77-8), oryzalin (597),oxadiargyl (599), oxadiazon (600), oxasulfuron (603), oxaziclomefone(604), oxyfluorfen (610), pebulate (617), pentachlorophenol (623),pentanochlor (624), pentoxazone (625), pethoxamid (627), petrolium oils(628), phenmedipham (629), picloram (645), picolinafen (646), piperophos(650), primisulfuron-methyl (657), prodiamine (661), profluazol (CAS RN190314-43-3), profoxydim (663), prohexadione calcium (664), prometon(665), prometryn (666), propachlor (667), propanil (669), propazine(672), propham (674), propisochlor (667), propoxycarbazone-sodium(procarbazone-sodium) (679), propyzamide (681), prosulfuron (684),pyraclonil (pyrazogyl) (CAS RN 158353-15-2), pyraflufen-ethyl (691),pyrazolynate (692), pyrazosulfuron-ethyl (694), pyrazoxyfen (695),pyribenzoxim (697), pyributicarb (698), pyridafol (CAS RN 40020-01-7),pyridate (702), pyriftalid (704), pyriminobac-methyl (707), pyrimisulfan(CAS RN 221205-90-9), pyrithiobac-sodium (709), quinmerac (713),quinoclamine (714), rimsulfuron (721), sequestrene, siduron (727),simazine (730), simetryn (732), sodium chlorate (734), sulfentrazone(749), sulfometuron-methyl (751), sulfosate (CAS RN 81591-81-3),sulfosulfuron (752), sulfuric acid (755), tar oils (758), TCA-sodium(760), tebutam (CAS RN 35256-85-0), tebuthiuron (765), tefuryltrione(CAS RN 473278-76-1), terbacil (772), terbumeton (774), terbutryn (776),thenylchlor (789), thidiazimin (CAS RN 123249-43-4), thiazafluoron (CASRN 25366-23-8), thiazopyr (793), thiobencarb (797), tiocarbazil (807),triaziflam (819), triclopyr (827), trietazine (831),triflusulfuron-methyl (837), trihydroxytriazine (CAS RN 108-80-5),trinexapac-ethyl (CAS RN 95266-40-3), tritosulfuron (843),N-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine(CAS RN 950782-86-2),1-(2-chloro-6-propylimidazo[1,2-b]pyridazin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea(CAS RN 570415-88-2), and5-(2,6-difluoro-benzyloxymethyl)-5-methyl-3-(3-methyl-thiophen-2-yl)-4,5-dihydro-isoxazole(CAS RN 403640-27-7).

The mixing partners of the compound of formula (I) may also be in theform of esters or salts, as mentioned e.g. in The Pesticide Manual, 13thEdition (BCPC), 2003. The reference to acifluorfen-sodium also appliesto acifluorfen, and the reference to bensulfuron-methyl also applies tobensulfuron, etc.

The mixing ratio of the compound of formula (I) to the mixing partner ispreferably from 1:100 to 1000:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula (I) with the mixing partner).

The compounds of formula (I) according to the invention can also be usedin combination with one or more safeners. Likewise, mixtures of acompound of formula (I) according to the invention with one or morefurther herbicides can also be used in combination with one or moresafeners. The term “safener” as used herein means a chemical that whenused in combination with a herbicide reduces the undesirable effects ofthe herbicide on non-target organisms, for example, a safener protectscrops from injury by herbicides but does not prevent the herbicide fromkilling the weeds. The safeners can be AD-67 (11), benoxacor (63),cloquintocet-mexyl (163), cyometrinil (CAS RN 78370-21-5),cyprosulfamide (CAS RN 221667-31-8), dichlormid (231), dicyclonon (CASRN 79260-71-2), fenchlorazole-ethyl (331), fenclorim (332), flurazole(386), fluxofenim (399), furilazole (413) and the corresponding Risomer, isoxadifen-ethyl (478), mefenpyr-diethyl (506),2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]-phenyl]sulfonyl]-benzamide(CAS RN 129531-12-0), naphthalic anhydride (CAS RN 81-84-5), andoxabetrinil (598). Particularly preferred are mixtures of a compound offormula (I) with benoxacor and a compound of formula (I) withcloquintocet-mexyl.

The safeners of the compound of formula (I) may also be in the form ofesters or salts, as mentioned e.g. in The Pesticide Manual, 13th Edition(BCPC), 2003. The reference to cloquintocet-mexyl also applies tocloquintocet, and the reference to fenchlorazole-ethyl also applies tofenchlorazole, etc.

Preferably the mixing ratio of compound of formula (I) to safener isfrom 100:1 to 1:10, especially from 20:1 to 1:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula (I) with the safener). It ispossible that the safener and a compound of formula (I) and one or moreadditional herbicide(s), if any, are applied simultaneously. Forexample, the safener, a compound of formula (I) and one or moreadditional herbicide(s), if any, might be applied to the locuspre-emergence or might be applied to the crop post-emergence. It is alsopossible that the safener and a compound of formula (I) and one or moreadditional herbicide(s), if any, are applied sequentially. For example,the safener might be applied before sowing the seeds as a seed treatmentand a compound of formula (I) and one or more additional herbicides, ifany, might be applied to the locus pre-emergence or might be applied tothe crop post-emergence.

Preferred mixtures of a compound of formula (I) with further herbicidesand safeners include:

Mixtures of a compound of formula (I) with S-metolachlor and a safener,particularly benoxacor.

Mixtures of a compound of formula (I) with isoxaflutole and a safener.

Mixtures of a compound of formula (I) with mesotrione and a safener.

Mixtures of a compound of formula (I) with sulcotrione and a safener.

Mixtures of a compound of formula (I) with a triazine and a safener.

Mixtures of a compound of formula (I) with a triazine and isoxaflutoleand a safener.

Mixtures of a compound of formula (I) with a triazine and mesotrione anda safener.

Mixtures of a compound of formula (I) with a triazine and sulcotrioneand a safener.

Mixtures of a compound of formula (I) with glyphosate and a safener.

Mixtures of a compound of formula (I) with glyphosate and isoxaflutoleand a safener.

Mixtures of a compound of formula (I) with glyphosate and mesotrione anda safener.

Mixtures of a compound of formula (I) with glyphosate and sulcotrioneand a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and asafener.

Mixtures of a compound of formula (I) with glufosinate-ammonium andisoxaflutole and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium andmesotrione and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium andsulcotrione and a safener.

Mixtures of a compound of formula (I) with florasulam and a safener,particularly cloquintocet-mexyl.

Mixtures of a compound of formula (I) with clodinafop-propargyl and asafener, particularly cloquintocet-mexyl.

Mixtures of a compound of formula (I) with pinoxaden and a safener,particularly cloquintocet-mexyl.

Mixtures of a compound of formula (I) with bromoxynil and a safener,particularly cloquintocet-mexyl.

The following Examples further illustrate, but do not limit, theinvention.

PREPARATION EXAMPLES

The following abbreviations were used throughout this section:s=singlet; bs=broad singlet; d=doublet; dd=double doublet; dt=doubletriplet; t=triplet, tt=triple triplet, q=quartet, sept=septet;m=multiplet; Me=methyl; Et=ethyl; Pr=propyl; Bu=butyl.

1. Reactions which are Covered by Scheme 1 Example 1.1 Preparation of2-amino-nicotinic acid methyl ester

To a solution of 3-amino-pyridine-2-carboxylic acid (1 g) in methanol (8ml) and toluene (10 ml), under nitrogen atmosphere, was added a solutionof (trimethylsilyl)-diazomethane (3.625 ml) (2M in diethylether). Whenthe effervescence from the reaction had subsided a further portion of(trimethylsilyl)diazomethane (3.625 ml) (2M in diethylether) was added.The reaction mixture was stirred at ambient temperature for 20 hours.The reaction was quenched by addition of acetic acid (0.2 ml). Themixture was concentrated and the residue partitioned betweendichloromethane and aqueous potassium carbonate (5% by weight). Thephases were separated and the aqueous phase was extracted with furtherdichloromethane. The combined organic extracts were dried over magnesiumsulfate and concentrated to give 2-amino-nicotinic acid methyl ester asa light yellow solid (968 mg). 1H-NMR (400 MHz, CDCl₃): 8.21-8.23 (m,1H), 8.12-8.14 (m, 1H), 6.61-6.64 (m, 1H), 3.89 (s, 3H) ppm.

The following compounds made were made using analogous procedures.

2-Amino-6-chloro-nicotinic acid methyl ester. 1H-NMR (400 MHz, CDCl₃):8.03-8.05 (d, 1H), 6.59-6.61 (d, 1H), 3.88 (s, 3H) ppm.

3-Amino-pyridine-2-carboxylic acid methyl ester. 1H-NMR (400 MHz,CDCl₃): 8.07-8.08 (m, 1H), 7.21-7.24 (m, 1H), 7.04-7.07 (m, 1H), 5.76(bs, 2H), 3.98 (s, 3H), ppm.

Example 1.2 Preparation of2-[2-(2,4-dichloro-phenyl)-acetylamino]-nicotinic acid methyl ester

Oxalyl chloride (0.14 ml) was added dropwise to a solution of(2,4-dichloro-phenyl)-acetic acid (270 mg) in dichloromethane (10 ml) atambient temperature. A drop of N,N-dimethylformamide (“DMF”) was addedto initiate the reaction. The reaction mixture was stirred at ambienttemperature for 2 hours. The reaction mixture was concentrated to give acolourless oil which was dissolved in dichloromethane (3 ml). Themixture was added dropwise to a cooled (−5° C.) slurry of2-amino-nicotinic acid methyl ester (200 mg) (Example 1.1),4-dimethylaminopyridine (“DMAP”) (32 mg) and pyridine (0.19 ml) indichloromethane (5 ml). The reaction mixture was allowed to warm toambient temperature and stirred at ambient temperature for 16 hours. Thereaction mixture was partitioned between dichloromethane and aqueoushydrochloric acid (2M). The phases were separated. The organic layer wasdried over magnesium sulfate and concentrated. The residue was purifiedby column chromatography on silica gel (eluent: acetone/iso-hexane ratio1:9 to 2:8) to give 2-[2-(2,4-dichloro-phenyl)-acetylamino]-nicotinicacid methyl ester as a light yellow gum (197 mg). 1H-NMR (400 MHz,CDCl₃): 10.81 (bs, 1H), 8.59-8.60 (m, 1H), 8.29-8.31 (m, 1H), 7.42-7.44(m, 1H), 7.34-7.36 (m, 1H), 7.23-7.27 (m, 1H), 7.07-7.11 (m, 1H), 4.08(s, 2H), 3.90 (s, 3H) ppm.

The following compounds made were made using analogous procedures.

2-[2-(2,6-Dichloro-phenyl)-acetylamino]-nicotinic acid methyl ester.1H-NMR (400 MHz, CDCl₃): 10.74 (bs, 1H), 8.59-8.61 (m, 1H), 8.28-8.31(m, 1H), 7.33-7.38 (m, 2H), 7.19-7.23 (m, 1H), 7.06-7.09 (m, 1H), 4.41(s, 2H), 3.89 (s, 3H) ppm.

2-[2-(2-Trifluoromethoxy-phenyl)-acetylamino]-nicotinic acid methylester. 1H-NMR (400 MHz, CDCl₃): 10.76 (bs, 1H), 8.57-8.59 (m, 1H),8.27-8.29 (m, 1H), 7.46-7.48 (m, 1H), 7.26-7.36 (m, 3H), 7.05-7.09 (m,1H), 4.03 (s, 2H), 3.88 (s, 3H) ppm.

2-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-nicotinic acid methylester. 1H-NMR (400 MHz, CDCl₃): 10.88 (bs, 1H), 8.59-8.60 (m, 1H),8.31-8.33 (m, 1H), 6.98-7.14 (m, 3H), 4.27 (s, 2H), 3.91 (s, 3H) ppm.

2-[2-(2,6-Diethyl-4-methyl-phenyl)-acetylamino]-nicotinic acid methylester. 1H-NMR (400 MHz, CDCl₃): 10.16 (bs, 1H), 8.59-8.61 (m, 1H),8.21-8.23 (dd, 1H), 7.04-7.07 (m, 1H), 6.97 (s, 2H), 3.94 (s, 2H), 3.78(s, 3H), 2.62-2.70 (m, 4H), 2.34 (s, 3H), 1.18-1.23 (t, 6H) ppm.

5-Bromo-2-[2-(2-chloro-3,6-difluoro-phenyl)-acetylamino]-nicotinic acid.1H-NMR (400 MHz, CDCl₃): 8.97 (d, 1H), 8.62-8.63 (d, 1H), 7.12-7.18 (m,1H), 7.03-7.08 (m, 1H), 4.31 (s, 2H) ppm.

6-Chloro-2-[2-(2-chloro-3,6-difluoro-phenyl)-acetylamino]-nicotinic acidmethyl ester. 1H-NMR (400 MHz, CDCl₃): 10.88 (bs, 1H), 8.23-8.25 (d,1H), 7.05-7.11 (m, 1H), 7.05-7.07 (d, 1H), 6.96-7.03 (m, 1H), 4.34 (s,2H), 3.92 (s, 3H) ppm.

3-[2-(2,4-Dichloro-phenyl)-acetylamino]-pyridine-2-carboxylic acidmethyl ester. 1H-NMR (400 MHz, CDCl₃): 11.04 (bs, 1H), 9.09-9.11 (dd,1H), 8.42-8.43 (dd, 1H), 7.47-7.50 (m, 2H), 7.29-7.37 (m, 2H), 3.99 (s,3H), 3.91 (s, 2H) ppm.

3-[2-(2-Trifluoromethoxy-phenyl)-acetylamino]-pyridine-2-carboxylic acidmethyl ester. 1H-NMR (400 MHz, CDCl₃): 11.04 (bs, 1H), 9.10 (dd, 1H),8.41 (dd, 1H), 7.30-7.50 (m, 5H), 3.90 (s, 3H), 3.89 (s, 2H) ppm.

3-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-pyridine-2-carboxylicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 11.09 (bs, 1H), 9.08-9.09(dd, 1H), 8.42-8.43 (dd, 1H), 7.46-7.50 (m, 1H), 7.05-7.18 (m, 2H), 4.03(s, 2H), 3.99 (s, 3H) ppm.

3-[2-(2,6-Diethyl-4-methyl-phenyl)-acetylamino]-pyridine-2-carboxylicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 10.62 (bs, 1H), 9.10-9.12(dd, 1H), 8.38-8.39 (dd, 1H), 7.44-7.47 (m, 1H), 6.98 (s, 2H), 3.88 (s,3H), 3.87 (s, 2H), 2.63-2.68 (q, 4H), 2.35 (s, 3H), 1.21 (t, 6H) ppm.

4-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-nicotinic acid methylester. 1H-NMR (400 MHz, CDCl₃): 11.27 (bs, 1H), 9.15 (s, 1H), 8.60 (s,2H), 7.13-7.19 (m, 1H), 7.05-7.11 (m, 1H), 4.04 (s, 2H), 3.94 (s, 3H)ppm.

3-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-isonicotinic acid ethylester. 1H-NMR (400 MHz, CDCl₃): 10.80 (bs, 1H), 10.00 (s, 1H), 8.44 (d,1H), 7.79-7.80 (d, 1H), 7.12-7.18 (m, 1H), 7.05-7.11 (m, 1H), 4.41-4.55(q, 2H), 4.04 (s, 2H), 1.40-1.43 (t, 3H) ppm.

6-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-[1,2,4]triazine-5-carboxylicacid ethyl ester. 1H-NMR (400 MHz, CDCl₃): 10.14 (bs, 1H), 9.64 (s, 1H),7.12-7.17 (m, 1H), 7.02-7.08 (m, 1H), 4.47-4.52 (q, 2H), 4.31 (s, 2H),1.45 (t, 3H) ppm.

4-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-pyrimidine-5-carboxylicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 10.94 (bs, 1H), 9.19 (s,1H), 9.06 (s, 1H), 7.00-7.15 (m, 2H), 4.40 (s, 2H), 3.98 (s, 3H) ppm.

2-[2-(2-Chloro-3,6-difluoro-phenyl)-acetylamino]-6-trifluoromethyl-nicotinicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 10.82 (bs, 1H), 8.52 (d,1H), 7.07-7.13 (m, 1H), 6.99-7.04 (m, 1H), 4.46 (s, 2H), 3.99 (s, 3H)ppm.

2-[2-(3-Bromo-2-chloro-6-fluoro-phenyl)-acetylamino]-nicotinic acidmethyl ester. 1H-NMR (400 MHz, CDCl₃): 10.84 (bs, 1H), 8.57-8.58 (d,1H), 8.30 (d, 1H), 7.55-7.58 (m, 1H), 7.06-7.09 (m, 1H), 6.94-6.97 (m,1H), 4.33 (s, 2H), 3.91 (s, 3H) ppm.

2-{[2-(2,3-Dichloro-6-fluoro-phenyl)-acetyl]-ethyl-amino}-4-methoxy-nicotinicacid ethyl ester. 1H-NMR (400 MHz, CDCl₃): 8.56-8.57 (d, 1H), 7.30-7.34(m, 1H), 6.96-7.00 (m, 1H), 6.90-6.93 (d, 1H), 4.39-4.44 (q, 2H), 3.97(s, 3H) 3.90-3.96 (m, 2H), 3.67 (s, 2H), 1.35-1.39 (t, 3H), 1.14-1.18(t, 3H) ppm.

Example 1.3 Preparation of 2-(2-pyridin-2-yl-acetylamino)-nicotinic acidmethyl ester

To a solution of 2-pyridyl-acetic acid hydrochloride (310 mg) and2-amino-nicotinic acid methyl ester (270 mg) (Example 1.1) indichloromethane (5 ml) was added diisopropylethylamine (0.32 ml). Thereaction mixture was stirred at ambient temperature for 20 minutes. Tothis solution was added 4-dimethylaminopyridine (43 mg) andN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (“EDAC”)(410 mg). The reaction mixture was stirred at ambient temperature for 20hours. The reaction mixture was partitioned between dichloromethane andwater. The phases were separated and the organic layer concentrated. Theresidue was purified by column chromatography on silica gel (eluent: 15%acetone in dichloromethane) to give2-(2-pyridin-2-yl-acetylamino)-nicotinic acid methyl ester as a yellowsolid (86 mg). 1H-NMR (400 MHz, CDCl₃): 11.14 (bs, 1H), 8.63-8.64 (m,1H), 8.58-8.59 (dd, 1H), 8.25-8.27 (dd, 1H), 7.66-7.70 (m, 1H), 7.38 (d,1H), 7.20-7.23 (m, 1H), 7.05-7.08 (dd, 1H), 4.11 (s, 2H), 3.92 (s, 3H)ppm.

The following compounds were made using analogous procedures:

3-(2-Pyridin-2-yl-acetylamino)-pyridine-2-carboxylic acid methyl ester.1H-NMR (400 MHz, CDCl₃): 11.36 (bs, 1H), 9.10-9.12 (dd, 1H), 8.67-8.69(m, 1H), 8.40-8.41 (dd, 1H), 7.69-7.73 (m, 1H), 7.45-7.48 (m, 1H),7.36-7.37 (m, 1H), 7.24-7.27 (m, 1H), 4.01 (s, 3H), 4.00 (s, 2H) ppm.

Example 1.4 Preparation of3-(2,4-dichloro-phenyl)-4-hydroxy-1H-[1,8]naphthyridin-2-one (CompoundD1 of Table D)

A mixture of 2-[2-(2,4-dichloro-phenyl)-acetylamino]-nicotinic acidmethyl ester (190 mg) (Example 1.2) and potassium carbonate (1 g) inN,N-dimethylformamide (5 ml) was heated to 110° C. for 5 hours. Thereaction mixture was allowed to cool to ambient temperature and thenstored at ambient temperature for 16 hours. Water (5 ml) was added tothe reaction mixture and the mixture acidified with potassium hydrogensulfate (1M in water). The precipitate was isolated and washedsuccessively with water and diethylether and dried to give Compound D1of Table D as a beige solid (74 mg).

The following compounds made were made using analogous procedures:

6-(2-Chloro-3,6-difluoro-phenyl)-5-hydroxy-8H-pyrido[2,3-d]pyrimidin-7-one.1H-NMR (400 MHz, d₆-DMSO): 10.97 (bs, 1H), 8.93 (s, 1H), 8.78 (s, 1H),7.26-7.32 (m, 1H), 7.12-7.18 (m, 1H) ppm.

Compound Nos. A1, A2 and A8 of Table A, Compound No. B2 of Table B,Compound Nos. D2, D3, D4, D12, D14 and D33 of Table D and Compound No.E4 of Table E.

Example 1.5 Preparation of4-Hydroxy-3-pyridin-3-yl-1H-[1,8]naphthyridin-2-one (Compound No. D11 ofTable D)

To a solution of 2-amino-nicotinic acid methyl ester (200 mg) (Example1.1) in N,N-dimethylformamide (“DMF”) (2 ml) was added sodium ethoxide(21 μl) (21% by weight in ethanol) followed by ethyl-3-pyridyl-acetate(200 μl). The reaction mixture was heated in the microwave at 150° C.for 15 minutes. The mixture was quenched by addition of aqueoushydrochloric acid (2M) (0.72 ml) and then diluted with water. Theprecipitate was isolated by filtration and washed with water and finallytriturated with diethyl ether to give4-hydroxy-3-pyridin-3-yl-1H-[1,8]naphthyridin-2-one as a beige solid(109 mg). 1H-NMR (400 MHz, d₆-DMSO): 11.75 (bs, 1H), 8.70 (m, 1H),8.52-8.53 (dd, 1H), 8.48-8.49 (dd, 1H), 8.35-8.37 (dd, 1H), 7.98 (d,1H), 7.45-7.49 (dd, 1H), 7.23-7.26 (dd, 1H) ppm.

The following compound was made using an analogous procedure:

Compound No. A7 of Table A.

Example 1.6 Preparation of 2,2-dimethyl-propionic acid3-(2-chloro-3,6-difluoro-phenyl)-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester

Compound D4 of Table D (1.487 g) and pyridine (0.978 ml) were stirred indichloromethane (30 ml) at ambient temperature for 5 minutes.2,2-Dimethylpropionyl chloride (0.21 ml) was added portionwise over aperiod of 10 minutes and the reaction stirred at ambient temperature fora further 3 hours. The reaction mixture was diluted with dichloromethaneand washed successively with water, aqueous sodium hydrogen carbonate(1M) and aqueous hydrochloric acid (2M). The organic layer was driedover magnesium sulfate and concentrated. The residue was purified bycolumn chromato-graphy on silica gel (eluent: ethyl acetate/hexane 1:1)to give 2,2-dimethyl-propionic acid3-(2-chloro-3,6-difluoro-phenyl)-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester as a white solid (764 mg). 1H-NMR (400 MHz, CDCl₃): 11.61 (bs,1H), 8.80-8.81 (d, 1H), 7.85-7.87 (d, 1H), 7.29-7.30 (d, 1H), 7.19-7.24(m, 1H), 7.06-7.10 (m, 1H), 1.16 (s, 9H) ppm.

The following compounds were made using analogous procedures:

Isobutyric acid3-(3-bromo-2-chloro-6-fluoro-phenyl)-2-hydroxy-[1,8]naphthyridin-4-ylester. 1H-NMR (400 MHz, CDCl₃): 12.04 (bs, 1H), 8.82-8.84 (d, 1H),7.89-7.91 (d, 1H), 7.67-7.71 (m, 1H), 7.26-7.30 (m, 1H), 7.01-7.05 (t,1H), 2.71 (sept, 1H), 1.08-1.09 (d, 3H), 1.06-1.07 (d, 3H) ppm.

Compound No. B3 of Table B, Compound No. D15 of Table D, Compound Nos.E1 and E5 of Table E.

2. Reactions which are Covered by Scheme 2 Example 2.1 Preparation of3-(2-chloro-3,6-difluoro-phenyl)-1-(2,2-difluoro-ethyl)-4-hydroxy-1H-[1,8]naphthyridin-2-one(Compound No. D21 of Table D)

A mixture of 2,2-dimethyl-propionic acid3-(2-chloro-3,6-difluoro-phenyl)-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester (Example 1.5) (0.2 g), potassium carbonate (0.211 g) and1-bromo-2,2-difluoro-ethane (0.15 g) in N,N-dimethylformamide (3 ml) washeated to 120° C. in a microwave for 15 minutes. The reaction mixturewas partitioned between ethyl acetate and water. The phases wereseparated and the organic phase was dried over magnesium sulfate andconcentrated. The residue was purified by column chromatography onsilica gel (eluent: ethyl acetate/hexane 1:1) to give Compound No. D21of Table D as a colourless oil (24 mg).

The following compounds made were made using analogous procedures:Compound Nos. D17 and D32 of Table D and Compound No. E6 of Table E.

Example 2.2 Preparation of isobutyric acid3-(2,6-diethyl-4-methyl-phenyl)-1-methyl-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester (Compound No. D6 of Table D)

To a solution of Compound No. D23 of Table D (100 mg) (Example 3.2) intetrahydrofuran (5 ml) was added potassium tert-butoxide (0.38 ml) (1Min tetrahydro-furan). The reaction mixture was stirred at ambienttemperature for 30 minutes. To this mixture was added isobutyrylchloride (42 μl) and the reaction mixture stirred for at ambienttemperature 2 hours. The reaction mixture was concentrated and theresidue purified by column chromatographed on silica gel (eluent: 1%ethyl acetate/dichloro-methane) to give Compound No. D6 of Table D as awhite solid (110 mg).

The following compounds made were made using analogous procedures:Compound Nos. A4 to A6 of Table A and Compound Nos. D7 to D9 of Table D.

Example 2.3 Preparation of 2,2-dimethyl-propionic acid3-(2-chloro-3,6-difluoro-phenyl)-1-(2,2-difluoro-ethyl)-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester (Compound No. D10 of Table D)

To a solution of Compound No. D24 of Table D (Example 2.1) (300 mg) inacetonitrile (3 ml) was added 4-dimethylaminopyridine (“DMAP”) (10 mg)and 2,2-dimethyl-propionyl chloride (0.21 ml). The reaction mixture washeated in a microwave for 1500 seconds at 150° C. The reaction mixturewas concentrated and the residue purified by column chromatography onsilica gel (eluent: ethyl acetate/hexane 1:4) to give Compound No. D10of Table D (24 mg).

The following compounds made were made using analogous procedures:Compound No. B5 of Table B, Compound No. C2 of Table C, Compound Nos.D16 and D19 of Table D.

Example 2.4 Preparation of 2,2-dimethyl-propionic acid3-(2-chloro-3,6-difluoro-phenyl)-1-ethyl-2-oxo-1,2-dihydro-[1,6]naphthyridin-4-ylester (Compound No. B1 of Table B)

To a solution of 2,2-dimethyl-propionic acid3-(2-chloro-3,6-difluoro-phenyl)-2-oxo-1,2-dihydro-[1,6]naphthyridin-4-ylester (250 mg) in acetonitrile (1.5 ml) was added potassium carbonate(88 mg) followed by methyl iodide (51 μl). The reaction mixture washeated to 100° C. for 22 minutes in a microwave and then cooled toambient temperature. The reaction mixture was diluted with ethyl acetateand water. The phases were separated. The organic fraction was washedwith water and brine, dried over magnesium sulfate and concentrated. Theresidue was purified by column chromatography on silica gel (eluent:ethyl acetate/hexane 1:3 and then 1:1) to give Compound No. B1 of TableB as an orange oil (16 mg). 1H-NMR (400 MHz, CDCl₃): 8.84 (s, 1H), 8.71(d, 1H), 7.32 (d, 1H), 7.18-7.23 (m, 1H), 7.05-7.10 (m, 1H), 4.38 (q,2H), 1.41 (t, 3H), 1.16 (s, 9H) ppm.

The following compounds made were made using analogous procedures:Compound No. D30 of Table D, and Compound Nos. E2 and E3 of Table E.Furthermore, Compound No. D31 of Table D was isolated as a by-product ofCompound No. D30 of Table D.

Example 2.5 Preparation of isobutyric acid3-(3-bromo-2-chloro-6-fluoro-phenyl)-1-(2,2-difluoro-ethyl)-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester (Compound No. D23 of Table D)

To a solution of Isobutyric acid3-(3-bromo-2-chloro-6-fluoro-phenyl)-2-hydroxy-[1,8]naphthyridin-4-ylester (1.749 g) in acetonitrile (17 ml) was addedN,N-diisopropylethylamine (“Hunig's base”) (0.83 ml) at ambienttemperature. The mixture was stirred for 5 minutes at ambienttemperature before drop wise addition of a solution of2,2-difluoroethyltrifluoromethanesulfonate (1.022 g) at ambienttemperature. The reaction mixture was stirred at ambient temperature for7 hours when further 2,2-difluoroethyltrifluoromethanesulfonate (0.5 g)and the reaction was stirred overnight. A further portion of2,2-difluoroethyltrifluoromethanesulfonate (0.5 g) andN,N-diisopropylethylamine (“Hunig's base”) (0.83 ml) was added and thereaction was stirred for 5 hours then left to stand overnight. Thereaction was concentrated and partitioned between ethyl acetate and 2Mhydrochloric acid. The organic layer was dried and concentrated and theoily residue was purified by column chromatography on silica (eluent:4:1 hexane:ethyl acetate) to give Compound No. D23 of Table D as a lightyellow solid (1.56 g).

3. Reactions which are Covered by Scheme 3 Example 3.1 Preparation of2-{[2-(2,6-diethyl-4-methyl-phenyl)-acetyl]-methyl-amino}-nicotinic acidmethyl ester

To a solution of2-[2-(2,6-diethyl-4-methyl-phenyl)-acetylamino]-nicotinic acid methylester (Example 1.2) (460 mg) in N,N-dimethylformamide (5 ml) was addediodomethane (0.42 ml) at between −5° C. and 0° C. under a nitrogenatmosphere. The reaction mixture was stirred for 2 minutes before theaddition of sodium hydride (60 mg) (60% by weight dispersion in mineraloil) in one portion at between −5° C. and 0° C. The reaction mixture wasstirred at between −5° C. and 0° C. for 1 hour, and then at ambienttemperature for 2 hours. The reaction mixture was partitioned betweendiethylether and aqueous hydrochloric acid (2M). The phases wereseparated and the organic phase was washed with brine, dried overmagnesium sulfate and concentrated. The residue was purified by columnchromatography on silica gel (eluent: 10% ethyl acetate/dichloromethane)to give2-{[2-(2,6-diethyl-4-methyl-phenyl)-acetyl]-methyl-amino}-nicotinic acidmethyl ester as a light orange oil (370 mg). 1H-NMR (400 MHz, CDCl₃):8.76 (m, 1H), 8.36-8.38 (m, 1H), 7.44-7.47 (m, 1H), 6.83 (s, 2H), 3.97(s, 3H), 3.33 (bs, 2H), 3.27 (bs, 3H), 2.47-2.57 (m, 4H), 2.26 (bs, 3H),1.09-1.12 (m, 6H) ppm.

The following compounds made were made using analogous procedures.

2-{[2-(2-Chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-nicotinicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 8.76-8.77 (m, 1H), 8.41-8.44(m, 1H), 7.49-7.52 (m, 1H), 6.88-7.06 (m, 2H), 3.98 (s, 3H), 3.56 (s,2H), 3.28 (s, 3H) ppm.

5-Bromo-2-{[2-(2-chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-nicotinicacid methyl ester. The crude compound was used directly for furthersynthesis.

3-{[2-(2-Chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-pyridine-2-carboxylicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 8.79-8.80 (m, 1H), 7.81-7.83(m, 1H), 7.63-7.66 (m, 1H), 6.91-7.11 (m, 2H), 4.03 (s, 3H), 3.55-3.59(m, 2H), 3.28 (s, 3H) ppm.

3-{[2-(2,6-Diethyl-4-methyl-phenyl)-acetyl]-methyl-amino}-pyridine-2-carboxylicacid methyl ester. 1H-NMR (400 MHz, CDCl₃): 8.76-8.78 (dd, 1H),7.71-7.74 (dd, 1H), 7.59-7.62 (m, 1H), 6.82 (s, 2H), 4.03 (s, 3H), 3.67(s, 2H), 3.26 (s, 3H), 2.45 (q, 4H), 2.26 (s, 3H), 1.11 (t, 6H) ppm.

3-{[2-(2-Chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-isonicotinicacid ethyl ester. 1H-NMR (400 MHz, CDCl₃): 8.75-8.76 (d, 1H), 8.69 (d,1H), 7.82-7.84 (dd, 1H), 6.93-7.03 (m, 1H), 6.85-6.90 (m, 1H), 4.35-4.42(m, 2H), 3.40 (s, 2H), 3.20 (s, 3H), 1.32-1.36 (t, 3H) ppm.

2-{[2-(2-Chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-6-trifluoromethyl-nicotinicacid methyl ester used crude in the next step

Example 3.2 Preparation of3-(2,6-diethyl-4-methyl-phenyl)-4-hydroxy-1-methyl-1H-[1,8]naphthyridin-2-one(Compound No. D20 of Table D)

To a solution of2-{[2-(2,6-diethyl-4-methyl-phenyl)-acetyl]-methyl-amino}-nicotinic acidmethyl ester (300 mg) in N,N-dimethylformamide (5 ml) was addedpotassium tert-butoxide (250 mg). The reaction mixture was stirred atambient temperature for 18 hours, and then at 50° C. for 2 hours. Thereaction mixture was partitioned the reaction between water anddichloromethane. The phases were separated and the aqueous phase wasextracted with further dichloromethane and ethyl acetate. The aqueousphase was acidified by addition of aqueous hydrochloric acid (2M) andextracted three times with ethyl acetate. The combined organic extractswere dried over magnesium sulfate and concentrated. The residue waspassed through a plug of silica eluting with ethyl acetate to giveCompound No. D20 of Table D as an off-white solid (320 mg).

The following compounds made were made using analogous procedures:

3-(2,6-Diethyl-4-methyl-phenyl)-4-hydroxy-1-methyl-1H-[1,5]naphthyridin-2-one.1H-NMR (400 MHz, CDCl₃): 8.50-8.51 (m, 1H), 7.76-7.78 (m, 1H), 7.59-7.62(m, 1H), 7.01 (s, 2H), 3.75 (s, 3H), 2.36 (s, 3H), 2.34-2.46 (m, 4H),1.09 (t, 6H) ppm.

Compound No. A3 of Table A, Compound No. B4 of Table B, Compound No. C1of Table C, Compound Nos. D5, D18, D22, D26 and D29 of Table D.

Example 3.3 Preparation of 2,2-dimethyl-propionic acid6-bromo-3-(2-chloro-3,6-difluoro-phenyl)-1-methyl-2-oxo-1,2-dihydro-[1,8]naphthyridin-4-ylester (Compound No. D13 of Table D)

Sodium hexamethyldisilazide (“NaHMDS”) (1.78 ml) (1M in tetrahydrofuran)was added dropwise to a solution of5-bromo-2-{[2-(2-chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-nicotinicacid methyl ester (Example 3.1) (0.22 g) in tetrahydrofuran (5 ml) undera nitrogen atmosphere and heated to 40° C. for 2 hours.2,2-Dimethyl-propionyl chloride (0.3 ml) was added to the reactionmixture and the reaction mixture heated for a further hour. The reactionmixture was partitioned between dichloromethane and water. The phaseswere separated and the organic phase was concentated. The residue waspurified by column chromatography on silica gel (eluent: ethylacetate/hexane 1:4) to give Compound No. D13 of Table D as an off-whitesolid (16 mg).

4. Reactions that are Covered by Scheme 4 Example 4.1 Preparation of6-chloro-2-methylamino-nicotinic acid methyl ester

A solution of 2,6-dichloro-nicotinic acid methyl ester (1.5 g),methylamine (0.99 ml) (33% by weight in ethanol) anddiisopropylethylamine (“Hunig's base”) (1.38 ml) was heated in amicrowave for 10 minutes at 120° C. The reaction mixture was partitionedbetween ethyl acetate and water. The phases were separated and theorganic layer was concentrated. The residue was purified by columnchromatography on silica gel (eluent: ethyl acetate/hexane 1:9) to give6-chloro-2-methylamino-nicotinic acid methyl ester as a white solid (915mg). 1H-NMR (400 MHz, CDCl₃): 8.03 (bs, 1H), 7.99-8.01 (d, 1H),6.49-6.51 (d, 1H), 3.86 (s, 3H), 3.05-3.06 (d, 3H) ppm.

The following compounds made were made using analogous procedures.

2-Chloro-6-methyl-4-methylamino-nicotinic acid ethyl ester. 1H-NMR (400MHz, CDCl₃): 7.16 (bs, 1H), 6.32 (s, 1H), 4.35-4.40 (q, 2H), 2.67-2.89(d, 3H), 2.41 (s, 3H), 1.38-1.42 (t, 3H) ppm.

4-Chloro-6-methyl-2-methylamino-nicotinic acid ethyl ester 1H-NMR (400MHz, CDCl₃): 7.35 (bs, 1H), 6.46 (s, 1H), 4.35-4.40 (q, 2H), 3.00-3.01(d, 3H), 2.37 (s, 3H), 1.38-1.42 (t, 3H) ppm.

2-Ethylamino-4-methoxy-nicotinic acid ethyl ester. 1H-NMR (400 MHz,CDCl₃): 8.08-8.10 (d, 1H), 7.54 (bs, 1H), 6.15-6.17 (d, 1H), 4.31-4.36(q, 2H), 3.85 (s, 3H), 3.45-3.52 (m, 2H), 1.35-1.39 (t, 3H), 1.23-1.27(t, 3H) ppm.

Example 4.2 Preparation of4-chloro-2-{[2-(2-chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-6-methyl-nicotinicacid ethyl ester

Oxalyl chloride (0.19 ml) was added dropwise to a solution of(2-chloro-3,6-difluoro-phenyl)-acetic acid (373 mg) in dichloromethane(5 ml) at ambient temperature. A drop of N,N-dimethylformamide (“DMF”)was added to initiate the reaction. The reaction mixture was stirred atambient temperature for 1 hour. The reaction mixture was concentrated togive a colourless oil which was dissolved in dichloromethane (5 ml). Themixture was added dropwise to a slurry of4-chloro-6-methyl-2-methylamino-nicotinic acid ethyl ester (Example 4.1)(413 mg) and pyridine (0.16 ml) in dichloromethane (5 ml). The reactionmixture was stirred at ambient temperature for 16 hours. The reactionmixture was partitioned between dichloromethane and water. The phaseswere separated and the organic layer was concentrated. The residue waspurified by column chromatography on silica gel (eluent: ethylacetate/hexane 1:4) to give4-chloro-2-{[2-(2-chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-6-methyl-nicotinicacid ethyl ester as a yellow solid (299 mg). ¹H NMR (400 MHz, CDCl₃):7.32 (bs, 1H), 7.00-7.05 (m, 1H), 6.90-6.96 (m, 1H), 4.43-4.45 (m, 2H),3.66 (s, 2H), 3.24 (m, 3H), 2.60 (s, 3H), 1.37-1.40 (t, 3H) ppm.

The following compounds made were made using analogous procedures.

2-Chloro-4-{[2-(2-chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-6-methyl-nicotinicacid ethyl ester. ¹H NMR (400 MHz, CDCl₃): 7.13 (s, 1H), 7.02-7.08 (m,1H), 6.93-7.00 (m, 1H), 4.42-4.46 (m, 2H), 3.49-3.75 (m, 2H), 3.21 (s,3H), 2.64 (s, 3H), 1.38-1.42 (t, 3H) ppm.

6-Chloro-2-{[2-(2-chloro-3,6-difluoro-phenyl)-acetyl]-methyl-amino}-nicotinicacid methyl ester. The crude compound was used directly for furthersynthesis.

Furthermore, 2-amino-6-trifluoromethyl-nicotinic acid methyl ester canbe prepared according to WO 08/076,425 and 2-chloro-4-methoxy-nicotinicacid ethyl ester can be prepared following the method and references inJ. Org. Chem., Vol. 70, No. 16, 2005.

TABLE A Compounds of formula (A), where R³, R⁴ and R⁵ have the values asdescribed in the table below. (A)

1H-NMR (400 MHz, CDCl₃ Comp except where indicated; No. R³ R⁴ R⁵chemical shifts in ppm) A1 H 2,4-dichloro- HO— d₆-DMSO: 11.68 (bs, 1H),8.52 phenyl- (d, 1H), 7.63-7.74 (m, 3H), 7.45- 7.48 (dd, 1H), 7.36 (d,1H). A2 H 2-trifluoro- HO— d₆-DMSO: 11.64 (bs, 1H), 8.51- methoxy- 8.52(dd, 1H), 7.71-7.74 (m, phenyl- 1H), 7.62-7.65 (m, 1H), 7.47- 7.51 (m,1H), 7.41-7.43 (m, 3H). A3 Me 2-chloro-3,6- HO— d₆-DMSO: 11.79 (bs, 1H),8.61- difluoro- 8.62 (dd, 1H), 8.10 (dd, 1H), phenyl- 7.79-7.82 (m, 1H),7.51-7.57 (m, 1H), 7.35-7.40 (m, 1H), 3.64 (s, 3H). A4 Me 2-chloro-3,6-i-Pr—(CO)O— 7.57-7.59 (dd, 1H), 7.78 (dd, difluoro- 1H), 7.55-7.58 (m,1H), 7.18- phenyl- 7.24 (m, 1H), 7.05-7.10 (m, 1H), 3.78 (s, 3H), 2.82(sept, 1H), 1.13-1.16 (dd, 6H). A5 Me 2-chloro-3,6- t-Bu—(CO)O—8.57-8.58 (dd, 1H), 7.75-7.78 difluoro- (dd, 1H), 7.54-7.57 (m, 1H),phenyl- 7.17-7.23 (m, 1H), 7.04-7.10 (m, 1H), 3.78 (s, 3H), 1.21 (s,9H). A6 Me 2,6-diethyl-4- i-Pr—(CO)O— 8.66-8.67 (dd, 1H), 7.82-7.85methyl- (m, 1H), 7.57-7.61 (m, 1H), 6.97 phenyl- (s, 2H), 3.79 (s, 3H),2.71 (sept, 1H), 2.33-2.44 (m, 4H), 2.35 (s, 3H), 1.08-1.12 (m, 6H),0.93 (bs, 6H). A7 H 3-pyridyl- HO— d₆-DMSO: 11.75 (bs, 1H), 8.73 (m,1H), 8.52-8.54 (m, 2H), 7.99-8.01 (m, 1H), 7.73-7.75 (m, 1H), 7.63-7.67(m, 1H), 7.50- 7.53 (m, 1H). A8 H 2-pyridyl- HO— d₆-DMSO: 11.13 (bs,1H), 9.33.- 9.35 (m, 1H), 8.59-8.60 (m, 1H), 8.42-8.44 (m, 1H),8.10-8.14 (m, 1H), 7.58-7.60 (m, 1H), 7.47- 7.50 (m, 1H), 7.42-7.46 (m,1H). A9 H 2,4,6- HO— Described in WO 04/056824 trifluoro- (Compound No.13 of Table 128 phenyl- on page 62).

TABLE B Compounds of formula(B), where R³, R⁴ and R⁵ have the values asdescribed in the table below. (B)

1H-NMR (400 MHz, CDCl₃ except where Comp indicated; chemical No. R^(1a)R^(1b) R^(1c) R³ R⁴ R⁵ shifts in ppm) B1 H H H Et 2-chloro- t-Bu— 8.84(s, 1H), 8.71 (d, 3,6- (CO)O— 1H), 7.32 (d, 1H), difluoro- 7.18-7.23 (m,1H), phenyl- 7.05-7.10 (m, 1H), 4.38 (q, 2H), 1.41 (t, 3H), 1.16 (s,9H). B2 H H H H 2-chloro- HO— d₆-DMSO: 11.74 3,6- (bs, 1H), 8.97 (s,difluoro- 1H), 8.44-8.45 (d, phenyl- 1H), 7.39-7.45 (m, 1H), 7.22-7.26(m, 1H), 7.17-7.19 (d, 1H). B3 H H H H 2-chloro- t-Bu— 8.83 (s, 1H),8.61- 3,6- (CO)O— 8.63 (d, 1H), 7.23- difluoro- 7.28 (m, 2H), 7.09-phenyl- 7.14 (m, 1H), 1.16 (s, 9H). B4 Cl Me H Me 2-chloro- HO— 7.48 (s,1H), 7.34- 3,6- 7.40 (m, 1H), 7.18- difluoro- 7.23 (m, 1H), 3.70 phenyl-(s, 3H), 2.63 (s, 3H). B5 Cl Me H Me 2-chloro- t-Bu— 7.14 (s, 1H), 7.18-3,6- (CO)O— 7.23 (m, 1H), 7.06- difluoro- 7.10 (m, 1H), 3.76 phenyl- (s,3H), 2.66 (s, 3H), 1.03 (s, 9H).

TABLE C Compounds of formula (C), where R³, R⁴ and R⁵ have the values asdescribed in the table below. (C)

1H-NMR (400 MHz, CDCl₃ except Comp where indicated; chemical shifts inNo. R³ R⁴ R⁵ ppm) Cl Me 2-chloro- HO— d₆-DMSO: 8.76 (s, 1H), 8.34 (d,1H), 3,6- 7.82-7.83 (d, 1H), 7.10-7.16 (m, 1H), difluoro- 6.96-7.00 (m,1H), 3.63 (s, 3H). phenyl- C2 Me 2-chloro- i-Pr—(CO)O— 8.97 (s, 1H),8.55-8.56 (d, 1H), 7.42- 3,6- 7.43 (d, 1H), 7.19-7.25 (m, 1H), 7.05-difluoro- 7.11 (m, 1H), 3.88 (s, 3H), 2.68-2.75 phenyl- (m, 1H),1.07-1.10 (d, 6H). C3 H 2,4,6- HO— Described in WO 04/056824 trifluoro-(Compound No. 25 of Table 128 on phenyl- page 62).

TABLE D Compounds of formula (D), where R³, R⁴ and R⁵ have the values asdescribed in the table below. (D)

1H-NMR (400 MHz, CDCl₃ except where Comp indicated; chemical shifts No.R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ in ppm) D1 H H H H 2,4- HO— d₆-DMSO:8.54-8.56 (dd, dichloro- 1H), 8.22-8.29 (dd, 1H), phenyl- 7.69 (d, 1H),7.45-7.48 (dd, 1H), 7.34 (d, 1H), 7.25-7.28 (dd, 1H). D2 H H H H 2,6-HO— d₆-DMSO: 11.92 (bs, 1H), dichloro- 10.97 (bs, 1H), 8.56-8.58 phenyl-(dd, 1H), 8.31-8.33 (dd, 1H), 7.55 (d, 1H), 7.53 (s, 1H), 7.48-7.50 (m,1H), 7.27-7.28 (m, 1H). D3 H H H H 2- HO— d₆-DMSO: 11.84 (bs, 1H),trifluoro- 10.73 (bs, 1H), 8.54-8.55 methoxy- (dd, 1H), 8.32-8.35 (dd,phenyl- 1H), 7.49-7.51 (m, 1H), 7.40-7.44 (m, 3H), 7.25- 7.28 (m, 1H).D4 H H H H 2-chloro- HO— d₆-DMSO: 12.01 (bs, 1H), 3,6- 11.21 (bs, 1H),8.58-8.60 difluoro- (dd, 1H), 8.33-8.36 (dd, phenyl- 1H), 7.51-7.56 (m,1H), 7.33-7.38 (m, 1H), 7.28- 7.31 (m, 1H). D5 H H H Me 2-chloro- HO—d₆-DMSO: 11.29 (bs, 1H), 3,6- 8.73-8.75 (dd, 1H), 8.43- difluoro- 8.45(dd, 1H), 7.52-7.58 phenyl- (m, 1H), 7.34-7.40 (m, 2H), 3.68 (s, 3H). D6H H H Me 2,6- i-Pr— 8.65-8.67 (dd, 1H), 7.75- diethyl-4- (CO)O— 7.78(dd, 1H), 7.19-7.22 methyl- (m, 1H), 6.96 (s, 2H), 3.90 phenyl- (s, 3H),2.53 (sept, 1H), 2.30-2.45 (m, 7H), 1.11 (t, 6H), 0.90 (d, 6H). D7 H H HMe 2-chloro- i-Pr— 8.71-8.73 (dd, 1H), 7.87- 3,6- (CO)O- 7.90 (dd, 1H),7.17-7.27 difluoro- (m, 2H), 7.04-7.10 (m, phenyl- 1H), 3.92 (s, 3H),2.70 (sept, 1H), 1.06-1.09 (dd, 6H). D8 H H H Me 2,6- t-Bu— 8.66-8.67(dd, 1H), 7.71- diethyl-4- (CO)O— 7.73 (dd, 1H), 7.19-7.22 methyl- (m,1H), 6.95 (s, 2H), 3.91 phenyl- (s, 3H), 2.31-2.43 (m, 4H), 2.33 (s,3H), 1.10 (t, 6H), 0.99 (s, 9H). D9 H H H Me 2-chloro- t-Bu— 8.71-8.73(dd, 1H), 7.83- 3,6- (CO)O— 7.86 (dd, 1H), 7.24-7.27 difluoro- (m, 1H),7.17-7.23 (m, phenyl- 1H), 7.04-7.09 (m, 1H), 3.92 (s, 3H), 1.15 (t,9H). D10 H H H F₂HC— 2-chloro- t-Bu— 8.75-8.76 (dd, 1H), 7.91- H₂C— 3,6-(CO)O— 7.93 (dd, 1H), 7.32-7.37 difluoro- (m, 1H), 7.23-7.28 (m, phenyl-1H), 7.09-7.15 (m, 1H), 6.21-6.50 (tt, 1H), 5.05- 5.13 (m, 2H), 1.20 (t,9H). D11 H H H H 3-pyridyl- HO— d₆-DMSO: 11.75 (bs, 1H), 8.70 (m, 1H),8.52-8.53 (dd, 1H), 8.48-8.49 (dd, 1H), 8.35-8.37 (dd, 1H), 7.98 (d,1H), 7.45-7.49 (dd, 1H), 7.23-7.26 (dd, 1H). D12 H H H H 2-pyridyl- HO—— D13 H Br H Me 2-chloro- t-Bu— 8.72 (d, 1H), 7.89 (d, 1H), 3,6- (CO)O—7.18-7.23 (m, 1H), 7.04- difluoro- 7.09 (m, 1H), 3.88 (s, 3H), phenyl-1.15 (s, 9H). D14 H H Cl H 2-chloro- HO— d₄-MeOH: 8.34-8.36 (d, 3,6-1H), 7.30-7.32 (d, 1H), difluoro- 7.31-7.37 (m, 1H), 7.16- phenyl- 7.21(m, 1H). D15 H H Cl H 2-chloro- t-Bu— 9.10 (bs, 1H), 7.72-7.75 3,6-(CO)O— (d, 1H), 7.24-7.26 (d, 1H), difluoro- 7.19-7.24 (m, 1H), 7.05-phenyl- 7.10 (m, 1H), 1.14 (s, 9H). D16 H H Cl Me 2-chloro- t-Bu—7.75-7.77 (d, 1H), 7.23- 3,6- (CO)O— 7.25 (d, 1H), 7.18-7.23 (m,difluoro- 1H), 7.04-7.09 (m, 1H), phenyl- 3.88 (s, 3H), 1.14 (s, 9H).D17 H H Cl F₂HC— 2-chloro- HO— 8.43-8.45 (d, 1H), 7.39- H₂C— 3,6- 7.41(d, 1H), 7.33-7.39 (m, difluoro- 1H), 7.17-7.23 (m, 1H), phenyl-6.09-6.39 (tt, 1H), 4.81- 4.83 (m, 2H). D18 Cl H Me Me 2-chloro- HO—7.28 (s, 1H), 7.32-7.38 (m, 3,6- 1H), 7.17-7.22 (m, 1H), difluoro- 3.79(s, 3H), 2.60 (s, 3H). phenyl- D19 Cl H Me Me 2-chloro- t-Bu— 7.11 (s,1H), 7.17-7.22 (m, 3,6- (CO)O— 1H), 7.05-7.09 (m, 1H), difluoro- 3.89(s, 3H), 2.62 (s, 3H), phenyl- 1.01 (s, 9H). D20 H H H Me 2,6- HO—8.65-8.67 (m, 1H), 8.25- diethyl-4- 8.27 (dd, 1H), 7.19-7.22 methyl- (m,1H), 7.06 (s, 2H), 3.86 phenyl- (s, 3H), 2.31-2.48 (m, 4H), 2.38 (s,3H), 1.08 (t, 6H). D21 H H H F₂HC— 2-chloro- HO— 8.72 (d, 1H), 8.40-8.42(d, H₂C— 3,6- 1H), 7.32-7.35 (d, 1H), difluoro- 7.20-7.24 (m, 1H), 7.09-phenyl- 7.14 (m, 1H), 6.13-6.44 (tt, 1H), 4.94-5.02 (m, 2H). D22 H H ClMe 2-chloro- HO— d₄-MeOH: 8.40-8.43 (d, 3,6- 1H), 7.35-7.37 (d, 1H),difluoro- 7.32-7.38 (m, 1H), 7.17- phenyl- 7.22 (m, 1H), 3.75 (s, 3H).D23 H H H F₂HC— 3-bromo- i-Pr— 8.69 (d, 1H) 7.90-7.91 (d, H₂C— 2-chloro-(CO)O— 1H) 7.66-7.70 (m, 1H) 6-fluoro- 7.26-7.31 (m, 2H) 7.00- phenyl-7.04 (m, 1H), 6.15-6.46 (tt, 1H) 4.99-5.07 (m, 2H) 2.67-2.74 (m, 1H)1.06- 1.08 (m, 6H). D24 H H H Me 2,4,6- HO— — trimethyl- phenyl- D25 H HH H 3- HO— — methoxy- phenyl- D26 MeO— H H Et 2,3- HO— 9.28 (bs, 1H)8.59-8.60 (d, dichloro- 1H), 7.45-7.49 (m, 1H), 6-fluoro- 7.03-7.07 (m,1H), 6.79 (d, phenyl- 1H), 4.58-4.63 (q, 2H) 4.14 (s, 3H), 1.32-1.35 (t,3H). D27 H Br H H 2,6- HO— — difluoro- phenyl- D28 H Br H H 2,4,6- HO— —trifluoro- phenyl- D29 H H F₃C— Me 2-chloro- HO— 8.55 (d, 1H), 7.56 (d,1H), 3,6- 7.08-7.13 (m, 1H), 6.98- difluoro- 7.03 (m, 1H), 3.81 (s, 3H).phenyl- D30 H H F₃C— Me 2-chloro- t-Bu— 8.01 (d, 1H), 7.60 (d, 1H), 3,6-(CO)O— 7.20-7.26 (m, 1H), 7.06- difluoro- 7.11 (m, 1H), 3.93 (s, 3H)phenyl- 1.16 (s, 9H). D31 H H F₃C— H 2-chloro- t-Bu— 7.99 (d, 1H), 7.61(d, 1H), 3,6- (CO)O— 7.20-7.26 (m, 1H), 7.06- difluoro- 7.11 (m, 1H),1.16 (s, 9H). phenyl- D32 H H H F₂HC— 3-bromo- HO— 8.68-8.69 (d, 1H),8.36 (d, H₂C— 2-chloro- 1H), 7.66-7.69 (m, 1H), 6-fluoro- 7.29-7.32 (m,1H), 7.00- phenyl- 7.05 (m, 1H), 6.09-6.40 (tt, 1H), 4.91-4.99 (m, 2H).D33 H H H H 3-bromo- HO— d6-DMSO: 11.92 (bs, 1H), 2-chloro- 8.53-8.54(d, 1H), 8.27- 6-fluoro- 8.30 (d, 1H), 7.81-7.84 (m, phenyl- 1H),7.22-7.28 (m, 2H).

TABLE E Compounds of formula (E), where A¹, A², A³, A⁴, R³, R⁴ and R⁵have the values as described in the table below. (E)

1H-NMR (400 MHz, CDCl₃ except where Comp indicated; chemical No. A¹ A²A³ A⁴ R³ R⁴ R⁵ shifts in ppm) E1 —CH— N —CH— N H 2-chloro- t-Bu—d₆-DMSO: 13.29 3,6- (CO)O— (bs, 1H), 9.16 (s, difluoro- 1H), 8.99 (s,1H), phenyl- 7.63-7.68 (m, 1H), 7.44-7.50 (m, 1H), 1.07 (s, 9H). E2 —CH—N —CH— N Et 2-chloro- i-Pr— 9.20 (s, 1H), 8.99 (s, 3,6- (CO)O— 1H),7.24-7.29 (m, difluoro- 1H), 7.10-7.15 (m, phenyl- 1H), 4.59-4.65 (q,2H), 2.76 (sept, 1H), 1.43 (t, 3H), 1.14 (d, 3H), 1.12 (d, 3H). E3 —CH—N —CH— N F₂HC— 2-chloro- i-Pr— 9.22 (s, 1H), 8.94 (s, H₂C— 3,6- (CO)O—1H), 7.26-7.31 (m, difluoro- 1H), 7.11-7.16 (m, phenyl- 1H), 6.15-6.45(tt, 1H), 4.96-5.04 (m, 2H), 2.78 (sept, 1H), 1.12-1.15 (m, 6H). E4 N—CH— N N H 2-chloro- HO— d₆-DMSO: 12.96 3,6- (bs, 1H), 9.77 (s,difluoro- 1H), 7.56-7.62 (m, phenyl- 1H), 7.38-7.44 (m, 1H). E5 N —CH— NN H 2-chloro- Me— 9.70 (s, 1H), 9.54 3,6- (CO)O— (m, 1H), 7.28-7.33difluoro- (m, 1H), 7.11-7.16 phenyl- (m, 1H), 2.32 (s, 3H). E6 N —CH— NN Me 2-chloro- Me— 9.69 (s, 1H), 9.54 3,6- (CO)O— (m, 1H), 7.26-7.32difluoro- (m, 1H), 7.11-7.16 phenyl- (m, 1H), 4.03 (s, 3H), 2.32 (s,3H). E7 N —CH— N N H 2-chloro- HO— Described in 6-fluoro- WO 04/056829phenyl- (Compound No. 18 of Table 132 on page 64). E8 —CH— —CH— N N H2-chloro- HO— Described in 6-fluoro- WO 04/056825 phenyl (Compound No.42 of Table 129 on page 61). E9 N —CH— N N H 2,4,6- EtO— 9.68 (s, 1H),6.96 (s, trimethyl- (CO)O— 2H), 4.20-4.27 (q, phenyl- 2H), 2.33 (s, 3H),2.12 (s, 6H), 1.29 (t, 3H). E10 —CH— N —CH— N H 2,4,6- HO— Described intrifluoro- WO 04/056826 phenyl- (Compound No. 13 of Table 128 on page62). E11 N —CH— N N H 2,4,6- HO— Described in trifluoro- WO 04/056829phenyl- (Compound No. 13 of Table 132 on page 64). E12 N —CH— N N H2,4,6- HO— 9.59 (s, 1H), 6.97 (s, trimethyl- 2H), 2.34 (s, 3H), phenyl-2.31 (s, 6H). E13 —CH— N N —CH— H 2,4,6- HO— Described in trifluoro- WO04/056825 phenyl- (Compound No. 25 of Table 129 on page 61).

Biological Examples Example B1 Herbicidal Action

Seeds of a variety of test species were sown in sterilised standard soilin seed trays each having 96 cells. After cultivation for 8 to 9 dayscultivation (post-emergence) under controlled conditions in a climaticchamber (cultivation at 23/17° C., day/night; 13 hours light; 50-60%humidity), the plants were treated with an aqueous spray solution of1000 mg/l of the active ingredient dissolved in 10% DMSO (dimethylsulfoxide, CAS RN 67-68-5) as a solvent, equivalent to 1000 g/ha. Theplants were grown in the climatic chamber after application at (24/19°C., day/night; 13 hours light; 50-60% humidity) and watered twice daily.After 9 days until the test was evaluated (10=total damage to plant,0=no damage to plant)

TABLE B1 Application post-emergence Rate Comp No. (g/ha) STEME NAAOFAMARE SOLNI A1 1000 0 2 0 0 A2 1000 3 0 0 0 A3 1000 3 4 6 3 A4 1000 4 65 4 A5 1000 0 3 0 7 A6 1000 8 6 3 6 A7 1000 6 2 0 0 D5 1000 7 6 7 0 D61000 2 0 0 0 D7 1000 3 0 6 0 D8 1000 2 3 0 0 D9 1000 2 2 3 0 D20 1000 55 0 0 E4 1000 0 0 2 4 E6 1000 2 0 0 0 STEME = Stellaria media; NAAOF =Nasturtium officinale; AMARE = Amaranthus retroflexus; SOLNI = Solanumnigrum.

Compound Nos. A8 and A9 of Table A, Compound Nos. B2 and B3 of Table B,Compound No. C3 of Table C, Compound Nos. D1, D2, D3, D4, D11, D12, D15,D25, D27 and D28 of Table D, Compound Nos. E5, E7, E8, E10, E11 and E13of Table E were tested using the same protocol and showed little or nodamage to the test plants under the test conditions.

Example B2 Herbicidal Action

Seeds of a variety of test species were sown in standard soil in pots.After 8 days cultivation (post-emergence) under controlled conditions ina glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity),the plants were sprayed with an aqueous spray solution derived from theformulation of the technical active ingredient in acetone/water (50:50)solution containing 0.5% Tween 20 (polyoxyethelyene sorbitanmonolaurate, CAS RN 9005-64-5). The test plants were then grown in aglasshouse under controlled conditions in a glasshouse (at 24/16° C.,day/night; 14 hours light; 65% humidity) and watered twice daily. After13 days, the test was evaluated (10=total damage to plant; 0=no damageto plant).

TABLE B2 Application post-emergence Rate Comp No. (g/ha) SOLNI AMARESETFA ECHCG IPOHE B4 1000 2 0 0 0 2 C1 1000 0 0 0 0 2 C2 1000 2 3 0 0 5D10 1000 7 7 0 0 6 D14 1000 0 4 0 4 0 D16 1000 2 2 0 0 2 D17 1000 6 6 00 5 D18 1000 3 2 2 0 0 D21 1000 10 10 1 2 9 D22 1000 4 2 0 1 6 D23 10009 4 0 1 4 D24 1000 1 0 0 0 1 D26 1000 6 6 4 4 6 D29 1000 4 6 0 0 7 D301000 2 0 0 0 2 D31 1000 0 0 0 0 1 D32 1000 7 4 1 1 6 D33 1000 3 1 0 0 7E2 1000 4 5 0 2 2 E3 1000 5 7 0 0 1 E9 1000 0 0 9 10 1 E12 1000 1 5 1010 3 SOLNI = Solanum nigrum; AMARE = Amaranthus retroflexus; SETFA =Setaria faberi; ECHCG = Echinochloa crus-galli; IPOHE = Ipomeahederaceae.

Compound Nos. B1 and B5 of Table B, Compound Nos. D13 and D19 of TableD, and Compound No. E1 of Table E were tested using the same protocoland showed little or no damage to the test plants under the testconditions.

1. A method of controlling plants which comprises applying to the plantsor to the locus thereof a herbicidally effective amount of a compound offormula (I)

wherein A¹, A², A³ and A⁴ are independently C—R¹ or N, provided at leastone of A¹, A², A³ and A⁴ is N, and provided that if A¹ and A⁴ are bothN, A² and A³ are not both C—R¹; each R¹ is independently hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, halo, cyano, hydroxy, C₁-C₄alkoxy,C₁-C₄alkylthio, aryl or aryl substituted by one to five R⁶, which may bethe same or different, or heteroaryl or heteroaryl substituted by one tofive R⁶, which may be the same or different; R³ is hydrogen,C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₂-C₁₀alkenyl, C₂-C₄haloalkenyl,C₂-C₁₀alkynyl, C₂-C₄haloalkynyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₆alkyl-, C₁-C₁₀alkoxy-C₁-C₆alkyl-,C₁-C₁₀cyanoalkyl-, C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; R⁴ is aryl oraryl substituted by one to five R⁸, which may be the same or different,or heteroaryl or heteroaryl substituted by one to four R⁸, which may bethe same or different; R⁵ is hydroxy or a group which can be metabolisedto a hydroxy group; each R⁶, R⁷ and R⁸ is independently halo, cyano,nitro, C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl,hydroxy, C₁-C₁₀alkoxy, C₁-C₄haloalkoxy, C₁-C₁₀alkoxy-C₁-C₄alkyl-,C₃-C₇cycloalkyl, C₃-C₇cycloalkoxy, C₃-C₇cycloalkyl-C₁-C₄alkyl-,C₃-C₇cycloalkyl-C₁-C₄alkoxy-, C₁-C₆alkylcarbonyl-, formyl,C₁-C₄alkoxycarbonyl-, C₁-C₄alkylcarbonyloxy-, C₁-C₁₀alkylthio-,C₁-C₄haloalkylthio-, C₁-C₁-C₄haloalkylsulfinyl-, C₁-C₁₀alkylsulfonyl-,C₁-C₄haloalkylsulfonyl-, amino, C₁-C₁₀alkylamino-, di-C₁-C₁₀alkylamino-,C₁-C₁₀alkylcarbonylamino-, aryl or aryl substituted by one to three R¹³,which may be the same or different, heteroaryl or heteroaryl substitutedby one to three R¹³, which may be the same or different,aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein the aryl moiety issubstituted by one to three R¹³, which may be the same or different,heteroaryl-C₁-C₄alkyl- or heteroaryl-C₁-C₄alkyl- wherein the heteroarylmoiety is substituted by one to three R¹³, which may be the same ordifferent, aryloxy- or aryloxy-substituted by one to three R¹³, whichmay be the same or different, heteroaryloxy- orheteroaryloxy-substituted by one to three R¹³, which may be the same ordifferent, arylthio- or arylthio-substituted by one to three R¹³, whichmay be the same or different, or heteroarylthio- orheteroarylthio-substituted by one to three R¹³, which may be the same ordifferent; and each R¹³ is independently halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy; or a salt or N-oxide thereof.
 2. A methodaccording to claim 1 wherein up to three of A¹, A², A³ and A⁴ are N. 3.A method according to claim 1 wherein each R¹ is hydrogen, C₁-C₄alkyl,C₁-C₄haloalkyl, halo, cyano, hydroxy or C₁-C₄alkoxy.
 4. A methodaccording to claim 1 wherein R³ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl or C₂-C₄haloalkynyl.
 5. Amethod according to claim 1 wherein R⁴ is aryl or aryl substituted byone to five R⁸, which may be the same or different, and wherein the R⁴aryl group is phenyl.
 6. A method according to claim 1 wherein R⁵ ishydroxy, R⁹-oxy-, R¹⁰-carbonyloxy-, tri-R¹¹-silyloxy- orR¹²-sulfonyloxy-, wherein R⁹ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl,C₂-C₁₀alkynyl or aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein the arylmoiety is substituted by one to five substituents independently selectedfrom halo, cyano, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy; R¹⁰is C₁-C₁₀alkyl, C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkyl-C₁-C₁₀alkyl-,C₁-C₁₀haloalkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₄alkoxy-C₁-C₁₀alkyl-,C₁-C₄alkylthio-C₁-C₄alkyl-, C₁-C₁₀alkoxy, C₂-C₁₀alkenyloxy,C₂-C₁₀alkynyloxy, C₁-C₁₀alkylthio-, N—C₁-C₄alkyl-amino-,N,N-di-(C₁-C₄alkyl)-amino-, aryl or aryl substituted by one to threeR¹⁴, which may be the same or different, heteroaryl or heteroarylsubstituted by one to three R¹⁴, which may be the same or different,aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein the aryl moiety issubstituted by one to three R¹⁴, which may be the same or different,heteroaryl-C₁-C₄alkyl- or heteroaryl-C₁-C₄alkyl- wherein the heteroarylmoiety is substituted by one to three R¹⁴, which may be the same ordifferent, aryloxy- or aryloxy-substituted by one to three R¹⁴, whichmay be the same or different, heteroaryloxy- orheteroaryloxy-substituted by one to three R¹⁴, which may be the same ordifferent, arylthio- or arylthio-substituted by one to three R¹⁴, whichmay be the same or different, or heteroarylthio- orheteroarylthio-substituted by one to three R¹⁴, which may be the same ordifferent; each R¹¹ is independently C₁-C₁₀alkyl or phenyl or phenylsubstituted by one to five substituents independently selected fromhalo, cyano, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy; R¹² isC₁-C₁₀alkyl, C₁-C₁₀haloalkyl, or phenyl or phenyl substituted by one tofive substituents independently selected from halo, cyano, nitro,C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy; and each R¹⁴ is independentlyhalo, cyano, nitro, C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₁-C₁₀alkoxy,C₁-C₄alkoxy-carbonyl-, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio-,C₁-C₁₀alkylsulfinyl-, C₁-C₄haloalkyl-sulfinyl-, C₁-C₁₀alkylsulfonyl-,C₁-C₄haloalkylsulfonyl-, aryl or aryl substituted by one to fivesubstituents independently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy, or heteroaryl or heteroaryl substitutedby one to four substituents independently selected from halo, cyano,nitro, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy.
 7. A compound offormula (Ib)

wherein A¹, A², A³, A⁴ and R⁴ are as defined in claim 1 and R⁵ is agroup which can be metabolised to a hydroxy group; or a salt or N-oxidethereof.
 8. A compound according to claim 7, wherein one of A¹, A², A³and A⁴ is N.
 9. A compound according to claim 7, wherein each R¹ ishydrogen.
 10. A compound according to claim 7, wherein R⁴ is aryl oraryl substituted by one to four R⁸, which may be the same or different,and wherein the R⁴ aryl group is phenyl.
 11. A compound according toclaim 7, wherein R⁵ is C₁-C₄alkylcarbonyloxy-, C₁-C₄alkoxycarbonyloxy-or C₁-C₄alkylthiocarbonyloxy-.
 12. A compound according to claim 7 whichis: (b) a compound of formula (B)

where R^(1a), R^(1b), R^(1c), R³, R⁴ and R⁵ have the values as describedin the table below: Compound No. R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ B3 H H HH 2-chloro-3,6- t-Bu-(CO)O— difluoro-phenyl-

(d) a compound of formula (D)

where R^(1a), R^(1b), R^(1c), R³, R⁴ and R⁵ have the values as describedin the table below: Com- pound No. R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ D15 H HCl H 2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl-

or (e) a compound of formula (E)

where A¹, A², A³, A⁴, R³, R⁴ and R⁵ have the values as described in thetable below: Compound No. A¹ A² A³ A⁴ R³ R⁴ R⁵ E1 —CH— N —CH— N H2-chloro- t-Bu-(CO)O— 3,6-difluoro- phenyl- E5 N —CH— N N H 2-chloro-Me-(CO)O— 3,6-difluoro- phenyl-


13. A compound of formula (Ic)

wherein A¹, A², A³, A⁴ and R⁴ are as defined in claim 1 and R³ isC₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₆alkyl-, C₁-C₁₀alkoxy-C₁-C₆alkyl-,C₁-C₁₀cyanoalkyl-, C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; and R⁵ is agroup which can be metabolised to a hydroxy group; or a salt or N-oxidethereof.
 14. A compound according to claim 13, wherein one of A¹, A², A³and A⁴ is N.
 15. A compound according to claim 13, wherein each R¹ ishydrogen.
 16. A compound according to claim 13, wherein R³ is hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynylor C₂-C₄haloalkynyl.
 17. A compound according to claim 16, wherein R³ ishydrogen, methyl, ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl,allyl or propargyl.
 18. A compound according to claim 13, wherein R⁴ isaryl or aryl substituted by one to four R⁸, which may be the same ordifferent, and wherein the R⁴ aryl group is phenyl.
 19. A compoundaccording to claim 13, wherein R⁵ is R⁹-oxy-, R¹⁰-carbonyloxy-,tri-R¹¹-silyloxy- or R¹²-sulfonyloxy-, wherein R⁹ is C₁-C₁₀alkyl,C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl-wherein the aryl moiety is substituted by one to five substituentsindependently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy; R¹⁰ is C₁-C₁₀alkyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₁₀alkyl-, C₁-C₁₀haloalkyl, C₂-C₁₀alkenyl,C₂-C₁₀alkynyl, C₁-C₄alkoxy-C₁-C₁₀alkyl-, C₁-C₄alkylthio-C₁-C₄alkyl-,C₁-C₁₀alkoxy, C₂-C₁₀alkenyloxy, C₂-C₁₀alkynyloxy, N—C₁-C₄alkyl-amino-,N,N-di-(C₁-C₄alkyl)-amino-, aryl or aryl substituted by one to threeR¹⁴, which may be the same or different, heteroaryl or heteroarylsubstituted by one to three R¹⁴, which may be the same or different,aryl-C₁-C₄alkyl- or aryl-C₁-C₄alkyl- wherein the aryl moiety issubstituted by one to three R¹⁴, which may be the same or different,heteroaryl-C₁-C₄alkyl- or heteroaryl-C₁-C₄alkyl- wherein the heteroarylmoiety is substituted by one to three R¹⁴, which may be the same ordifferent, aryloxy- or aryloxy-substituted by one to three R¹⁴, whichmay be the same or different, heteroaryloxy- orheteroaryloxy-substituted by one to three R¹⁴, which may be the same ordifferent, arylthio- or arylthio-substituted by one to three R¹⁴, whichmay be the same or different, or heteroarylthio- orheteroarylthio-substituted by one to three R¹⁴, which may be the same ordifferent; each R¹¹ is independently C₁-C₁₀alkyl or phenyl or phenylsubstituted by one to five substituents independently selected fromhalo, cyano, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy; R¹² isC₁-C₁₀alkyl, C₁-C₁₀haloalkyl, or phenyl or phenyl substituted by one tofive substituents independently selected from halo, cyano, nitro,C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy; and each R¹⁴ is independentlyhalo, cyano, nitro, C₁-C₁₀alkyl, C₁-C₄haloalkyl, C₁-C₁₀alkoxy,C₁-C₄alkoxy-carbonyl-, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio-,C₁-C₁₀alkylsulfinyl-, C₁-C₄haloalkyl-sulfinyl-, C₁-C₁₀alkylsulfonyl-,C₁-C₄haloalkylsulfonyl-, aryl or aryl substituted by one to fivesubstituents independently selected from halo, cyano, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl or C₁-C₆alkoxy, or heteroaryl or heteroaryl substitutedby one to four substituents independently selected from halo, cyano,nitro, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy.
 20. A compoundaccording to claim 13, wherein R⁵ is C₁-C₄alkylcarbonyloxy-,C₁-C₄alkoxycarbonyloxy- or C₁-C₄alkylthiocarbonyloxy,
 21. A compoundaccording to claim 13 which is: (a) a compound of formula (A)

where R³, R⁴ and R⁵ have the values as described in the table below:Compound No. R³ R⁴ R⁵ A4 Me 2-chloro-3,6- i-Pr—(CO)O— difluoro-phenyl-A5 Me 2-chloro-3,6- t-Bu-(CO)O— difluoro-phenyl- A6 Me 2,6-diethyl-4-i-Pr—(CO)O— methyl-phenyl-

or (b) a compound of formula (B)

where R^(1a), R^(1b), R^(1c), R³, R⁴ and R⁵ have the values as describedin the table below: Com- pound No. R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ B1 H HH Et 2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl- B5 Cl Me H Me2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl-

or (c) a compound of formula (C)

where R³, R⁴ and R⁵ have the values as described in the table below:Compound No. R³ R⁴ R⁵ C2 Me 2-chloro-3,6- i-Pr—(CO)O— difluoro-phenyl-

or (d) a compound of formula (D)

where R^(1a), R^(1b), R^(1c), R³, R⁴ and R⁵ have the values as describedin the table below: Com- pound No. R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ D6 H HH Me 2,6-diethyl-4- i-Pr—(CO)O— methyl-phenyl- D7 H H H Me 2-chloro-3,6-i-Pr—(CO)O— difluoro- phenyl- D8 H H H Me 2,6-diethyl-4- t-Bu-(CO)O—methyl-phenyl- D9 H H H Me 2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl-D10 H H H F₂HC—H₂C— 2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl- D13 H BrH Me 2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl- D16 H H Cl Me2-chloro-3,6- t-Bu-(CO)O— difluoro- phenyl- D19 Cl H Me Me 2-chloro-3,6-t-Bu-(CO)O— difluoro- phenyl-

or (e) a compound of formula (E)

where A¹, A², A³, A⁴, R³, R⁴ and R⁵ have the values as described in thetable below: Com- pound No. A¹ A² A³ A⁴ R³ R⁴ R⁵ E2 —CH— N —CH— N Et2-chloro- i-Pr—(CO)O— 3,6-difluoro- phenyl- E3 —CH— N —CH— N F₂HC—H₂C—2-chloro- i-Pr—(CO)O— 3,6-difluoro- phenyl- E6 N —CH— N N Me 2-chloro-Me-(CO)O— 3,6-difluoro- phenyl- .


22. A compound of formula (Id)

wherein A¹, A², A³, A⁴ and R⁴ are as defined in claim 1 and R³ isC₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkyl-C₁-C₆alkyl-, C₁-C₁₀alkoxy-C₁-C₆alkyl-,C₁-C₁₀cyanoalkyl-, C₁-C₁₀alkoxycarbonyl-C₁-C₆alkyl-,N—C₁-C₃alkyl-aminocarbonyl-C₁-C₆alkyl-,N,N-di-(C₁-C₃alkyl)-aminocarbonyl-C₁-C₆alkyl-, aryl-C₁-C₆alkyl- oraryl-C₁-C₆alkyl- wherein the aryl moiety is substituted by one to threeR⁷, which may be the same or different, or heterocyclyl-C₁-C₆alkyl- orheterocyclyl-C₁-C₆alkyl- wherein the heterocyclyl moiety is substitutedby one to three R⁷, which may be the same or different; or a salt orN-oxide thereof.
 23. A compound according to claim 22, wherein one ofA¹, A², A³ and A⁴ is N.
 24. A compound according to claim 22, whereineach R¹ is hydrogen.
 25. A compound according to claim 22, wherein R³ ishydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl,C₂-C₄alkynyl or C₂-C₄haloalkynyl.
 26. A compound according to claim 25,wherein R³ is hydrogen, methyl, ethyl, 2,2-difluoro-ethyl,2,2,2-trifluoro-ethyl, allyl or propargyl.
 27. A compound according toclaim 22, wherein R⁴ is aryl or aryl substituted by one to four R⁸,which may be the same or different, and wherein the R⁴ aryl group isphenyl.
 28. A compound according to claim 22 which is: (a) a compound offormula (A)

where R³, R⁴ and R⁵ have the values as described in the table below:Compound No. R³ R⁴ R⁵ A3 Me 2-chloro-3,6- HO— difluoro-phenyl-

or (b) a compound of formula (B)

where R^(1a), R^(1b), R^(1c), R³, R⁴ and R⁵ have the values as describedin the table below: Com- pound No. R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ B4 ClMe H Me 2-chloro-3,6- HO— difluoro- phenyl-

or (c) a compound of formula (C)

where R³, R⁴ and R⁵ have the values as described in the table below:Compound No. R³ R⁴ R⁵ C1 Me 2-chloro-3,6- HO— difluoro-phenyl-

or (d) a compound of formula (D)

where R^(1a), R^(1b), R^(1c), R³, R⁴ and R⁵ have the values as describedin the table below: Com- pound No. R^(1a) R^(1b) R^(1c) R³ R⁴ R⁵ D5 H HH Me 2-chloro-3,6- HO— difluoro- phenyl- D17 H H Cl F₂HC—H₂C—2-chloro-3,6- HO— difluoro- phenyl- D18 Cl H Me Me 2-chloro-3,6- HO—difluoro- phenyl- D20 H H H Me 2,6-diethyl-4- HO— methyl-phenyl- D21 H HH F₂HC—H₂C— 2-chloro-3,6- HO— difluoro- phenyl- D22 H H Cl Me2-chloro-3,6- HO— difluoro- phenyl-


29. A herbicidal composition which comprises a herbicidally effectiveamount of a compound of formula (Ib), (Ic) or (Id), as defined in claim7 in addition to formulation adjuvants.
 30. A herbicidal compositionwhich comprises a herbicidally effective amount of a compound of formula(Ib), (Ic) or (Id), as defined in claim 7, optionally one or morefurther herbicides, and optionally one or more safeners.